Occurrence and Removal of Emerging 
Contaminants in Wastewaters 
 
 
A thesis submitted to Brunel University in fulfilment of the 
requirements for the degree of 
Doctor of Philosophy 
in  
Environmental Engineering 
by 
 
Hussein Janna 
B.Sc. Civil Engineering 
H.D. Water Pollution Control Engineering 
M.Sc. Environmental Engineering  
 
London, 2011
DECLARATION OF OWN WORK 
 
 
I declare that this PhD dissertation: 
 
 
Occurrence and Removal of Emerging Contaminants in Wastewaters 
 
 
is entirely my own work and that where any material could be construed as 
the work of others, it is fully cited and references, and/or with appropriate 
acknowledgement given. 
 
 
 
  
 
 
 
 
 
 
 
 
 
ii 
 
ABSTRACT 
Over the past decade, the occurrence and removal of emerging contaminants in the environment 
has received much attention. Both natural and synthetic progestogens, which are hormones, and 
also benzotriazoles are two examples of such emerging contaminants. Sewage treatment works 
are recognised as one of the main routes of these compounds to the environment. Low 
concentrations (nanograms per litre) of biologically active chemicals may exhibit an impact on 
aquatic organisms and human health. This study was undertaken to determine the occurrence 
and removal of these two classes of chemicals at sewage treatment works, along with an 
evaluation of the performance of advanced treatment and also to investigate their fate in the 
aquatic environment.  Therefore, field-based sampling campaigns were undertaken at a sewage 
treatment works, rivers and potable water to achieve these aims. Solid phase extraction and 
LC/MS/MS were used in order to analyse the samples from these different locations, along with 
catchment modelling and assessment of how the use of benzotriazoles may contribute to their 
presence in the environment. 
The results have demonstrated that progestogens and benzotriazoles are in the sewage system; 
the natural hormone (progesterone) was the most predominant compound entering the sewage 
treatment work (46.9 ng/l) among the progestogens while concentrations of the benzotriazoles 
were two orders of magnitude higher than the progestogens. The conventional sewage 
treatment works were, to some extent, able to remove these compounds from wastewaters. 
However, this may not be adequate to afford protection to the environment. The investigation of 
advanced treatments, ozone, granular activated carbon and chlorine dioxide, indicated no 
further significant removal of progestogens, probably as a result of concentrations being close to 
method detection limits. However, there were indications that benzotriazoles were removed. A 
degradation study demonstrated that the natural hormone (progesterone) was degraded rapidly 
while benzotriazoles were not degraded. Catchment modelling indicated that high (up to 2,000 
ng/l) concentrations of benzotriazoles would be present in surface waters used for potable 
supply, and consequently benzotriazoles were found in the tap water with mean concentrations 
of 30.9 ng/l (benzotriazole) and 15.1 ng/l for tolyltriazole. It is therefore apparent that although 
conventional treatment may be seen as effective, achieving over 90% removal, this may not be 
good enough. However, before investing in tertiary treatment, a number of factors, such as the 
effectiveness at different sites, the presence of degradation products and costs, both financial 
and in relation to energy use, need to be considered. 
 
iii 
 
ACKNOWLEDGMENTS 
First and foremost, I would like to present my thankfulness and greatest glory to ALLAH 
who gave me the courage and willingness to complete my thesis. 
I am immensely grateful to my academic supervisor Dr. Mark D. Scrimshaw for all his 
support, help and guidance throughout this PhD; I could not have done this without him. 
I would like to thank my second  supervisor  Dr. A. J. Chaudhary  for  his  scientific 
support and  guidance  during  my research. 
I am grateful for financial support obtained from sponsors that enabled me to achieve 
this study, the Ministry of Higher Education and Scientific Research (IRAQ), the 
Engineering and Physical Sciences Research Council (EPSRC) (UK) and Severn Trent 
Water Ltd. (UK). Without their financial support and help, the work presented here 
would not have been possible. 
I also would like to take this opportunity to thank the staff at the wastewater treatment 
plant, John Churchly, Michael and Emilie Cope for their help and efforts during the 
sampling campaigns. Moreover, I am deeply in debt to Richard Williams at Centre for 
Ecology and Hydrology (CEH) for his help with modelling. Special thanks goes to all staff, 
friends and colleagues at Brunel, for creating an unforgettable working environment and 
friendly atmosphere and also being my best ‘teachers’ of the English language. 
Finally, a great thank you to my family and relatives for their encouragement, love and 
support, especially my parents that have always been there for me.   I would  like  to 
thank  my  wife  for  being  patient,  loving and  caring since the second year of my PhD. I 
am grateful they gave me guidance and encouragement to be the person I should be.  
 
 
Hussein  
 
iv 
 
TABLE OF CONTENTS 
 
ABSTRACT .......................................................................................................................................................... ii 
ACKNOWLEDGMENTS ................................................................................................................................... iii 
TABLE OF CONTENTS .................................................................................................................................... iv 
LIST OF TABLES ............................................................................................................................................. viii 
LIST OF FIGURES ............................................................................................................................................... x 
LIST OF ABBREVIATIONS, UNITS AND SYMBOLS .............................................................................. xiii 
LIST OF PUBLICATIONS .............................................................................................................................. xvi 
Chapter One:  Introduction ....................................................................................................................... 1 
1.1 Introduction ................................................................................................................................ 2 
1.2 Aims and objectives .................................................................................................................. 4 
1.3 Thesis outline.............................................................................................................................. 5 
Chapter Two:  Literature Review ............................................................................................................ 6 
Overview ........................................................................................................................................................ 7 
2.1 Introduction ................................................................................................................................ 7 
2.2 The history of emerging contaminants in the aquatic environment ...................... 8 
2.3 Emerging contaminants in the aquatic environment. .................................................. 9 
2.3.1 Classification of contaminants. ........................................................................................ 9 
2.3.2 Sources and pathways of emerging contaminants. ................................................. 10 
2.3.3 Analytical methods to determine emerging contaminants in aquatic 
environment. ....................................................................................................................................... 12 
2.3.4 The occurrence of emerging contaminants in the aquatic environment. ...... 14 
2.3.5 The impact of emerging contaminants in the aquatic environment. ............... 15 
2.4 Overview of STW. ..................................................................................................................... 17 
2.4.1 Preliminary treatment. ..................................................................................................... 17 
2.4.2 Primary treatment. ............................................................................................................. 18 
2.4.3 Secondary treatment. ........................................................................................................ 18 
2.5 Removal mechanisms. ........................................................................................................... 20 
2.5.1 Biodegradation. ................................................................................................................... 20 
2.5.2 Sorption. ................................................................................................................................. 22 
2.5.3 Photolysis. .............................................................................................................................. 23 
2.5.4 Volatilization. ....................................................................................................................... 23 
2.6 Advanced treatment. .............................................................................................................. 24 
 
v 
 
2.6.1 Treatment by ozone (O3). ................................................................................................. 24 
2.6.2 Treatment by chlorine dioxide (ClO2). ........................................................................ 26 
2.6.3 Treatment by granular activated carbon (GAC). ..................................................... 27 
2.7 Selection of emerging contaminants in this study....................................................... 28 
2.7.1 Progestogens. ....................................................................................................................... 29 
2.7.2 Benzotriazoles. ..................................................................................................................... 30 
Chapter Three:  Materials, Methods, and Field Study Description ........................................... 31 
Overview ...................................................................................................................................................... 32 
3.1 Experimental method. ...................................................................................................................... 32 
3.1.1 Reagents and chemical .......................................................................................................... 32 
3.1.1.1 Analysed standards ............................................................................................................ 32 
3.1.1.2 Internal standards .............................................................................................................. 32 
3.1.1.3 Solvents and standard solutions.................................................................................... 33 
3.1.2 Reference standards preparation. .................................................................................... 33 
3.1.2.1 Progestogens ........................................................................................................................ 33 
3.1.2.2 Benzotriazoles ...................................................................................................................... 33 
3.1.3 Instrumentation ....................................................................................................................... 37 
3.1.3.1 LC/MS/MS method .............................................................................................................. 37 
3.1.3.2 Chromatography.................................................................................................................. 39 
3.1.4 Development of an analytical method for progestogens .......................................... 40 
3.1.4.1 Cartridges types ................................................................................................................... 41 
3.1.4.2 Slough data and validation .............................................................................................. 41 
3.1.5 Final analytical methods ....................................................................................................... 46 
3.1.5.1 Analytical method for progestogens ............................................................................ 46 
3.1.5.2 Analytical methods for benzotriazoles ....................................................................... 47 
3.1.6 Quality  control ......................................................................................................................... 49 
3.1.6.1 Limit of detection (LOD) and limit of quantification (LOQ) ................................. 49 
3.1.6.2 Blanks ...................................................................................................................................... 50 
3.1.6.3  Recoveries............................................................................................................................. 52 
3.2 Field studies. ........................................................................................................................................ 54 
3.2.1 Sampling of wastewater at Hallam Fields and Newthorpe .................................. 54 
3.2.2 Sampling of the Erewash River ...................................................................................... 57 
3.2.3 Sampling of tap water ........................................................................................................ 59 
3.2.4 Domestic dishwasher powders and tablets ............................................................... 59 
3.3 Degradation study ............................................................................................................................. 60 
 
vi 
 
3.4 Modelling .............................................................................................................................................. 61 
3.4.1 Overview of the model ........................................................................................................... 62 
3.4.2 Method of extrapolation to the Trent basin ................................................................... 62 
Chapter Four:  Results of Conventional Treatment ..................................................................... 66 
Overview ...................................................................................................................................................... 67 
4.1 Physiochemical parameters and sampling conditions. ............................................. 67 
4.2 Occurrence and removal of progestogens in conventional treatment works. .. 70 
4.2.1 Settled sewage ...................................................................................................................... 70 
4.2.2 Rapid gravity filter (RGF) feed. ...................................................................................... 72 
4.2.3 Final effluent ......................................................................................................................... 73 
4.3 Occurrence and removal of benzotriazoles in conventional treatment works. 74 
Chapter Five: Results of Advanced Treatments .............................................................................. 77 
Overview ...................................................................................................................................................... 78 
5.1 Operation parameters for ozone, granular activated carbon, and chlorine 
dioxide.........................................................................................................................................................78 
5.2 Occurrence and removal of progestogens in the advanced treatment processes.
 .......................................................................................................................................................79 
5.2.1 Removal by ozone ............................................................................................................... 79 
5.2.2 Removal by granular activated carbon (GAC). ......................................................... 80 
5.2.3 Removal by chlorine dioxide. ......................................................................................... 81 
5.3 Occurrence and removal of benzotriazoles in the advanced treatment process.
 .......................................................................................................................................................82 
5.3.1 Removal by ozone. .............................................................................................................. 83 
5.3.2 Removal by granular activated carbon (GAC). ......................................................... 83 
5.3.3 Removal by chlorine dioxide. ......................................................................................... 84 
Summary ...................................................................................................................................................... 85 
Chapter Six: The Fate of Progestogens and Benzotriazoles in the Laboratory 
Degradation Test ........................................................................................................................................... 86 
Overview ...................................................................................................................................................... 87 
6.1 Basic parameters and initial concentrations. ............................................................... 87 
6.2 Degradation of progestogens .............................................................................................. 88 
6.3 Degradation of benzotriazoles ........................................................................................... 93 
Summary ...................................................................................................................................................... 94 
Chapter Seven: Results of Monitoring and Modelling of Progestogens and Benzotriazoles 
in River Erewash, Trent and Thames Catchments ............................................................................ 96 
Overview ...................................................................................................................................................... 97 
 
vii 
 
7.1 Details of selected sewage treatment works. ................................................................ 97 
7.2 The occurrence of progestogens in the River Erewash. ............................................ 98 
7.3 Occurrence of benzotriazoles in River Erewash ....................................................... 100 
7.3.1 The first survey in January 2009 ................................................................................ 100 
7.3.2 The second survey in October 2009. ......................................................................... 102 
7.4 Modelling of the River Erewash ...................................................................................... 107 
7.5 Catchment modelling .......................................................................................................... 109 
7.5.1 Trent River catchment modelling. ............................................................................. 109 
7.5.2 Thames River catchment modelling.......................................................................... 110 
Summary ................................................................................................................................................... 111 
Chapter Eight: Results of the Occurrence and Possible Source of Benzotriazole and 
Tolyltriazole in Potable Water .............................................................................................................. 112 
Overview ................................................................................................................................................... 113 
8.1 Occurrence in drinking water .......................................................................................... 113 
8.2 Estimation of the inputs of BT and TT from dishwasher detergents ................. 116 
Summary ................................................................................................................................................... 117 
Chapter Nine: Discussion ....................................................................................................................... 119 
9.1 Occurrence and removal of emerging contaminants in conventional treatment
 ....................................................................................................................................................120 
9.1.1 Progestogens. .................................................................................................................... 120 
9.1.2 Benzotriazoles ................................................................................................................... 127 
9.1.3 The mechanism of removal of emerging contaminants during wastewater 
treatment. .......................................................................................................................................... 130 
9.1.4 The possible significance of these compounds in the environment .............. 131 
9.2 Occurrence and removal of emerging contaminants during advanced 
treatment .................................................................................................................................................. 133 
9.3 Is there a need to further remove emerging contaminants from effluents? ... 137 
Chapter Ten:  Conclusions ................................................................................................................... 142 
REFERENCES ................................................................................................................................................. 145 
Appendix 1:  Conventional Treatment ........................................................................................... 172 
Appendix 2:  Advanced Treatments ................................................................................................ 179 
Appendix 3:  Degradation Test ......................................................................................................... 182 
Appendix 4:  Modelling ........................................................................................................................ 189 
Appendix 5:  Drinking Water and Detergents ............................................................................. 192 
 
 
viii 
 
LIST OF TABLES 
Table 3.1 Details of selected progestogens and benzotriazoles………..……………………34 
Table 3.2 Retention time and masses for progestogens……………………………..…………38 
Table 3.3 Retention time and masses for benzotriazoles……………………………………...38 
Table 3.4 Mean recovery percentage of progestogens from different cartridges……41 
Table 3.5 Concentrations of target compounds at Slough sewage treatment work in 
(ng/l) (1st sampling)………..……………….………………………………………………….42 
Table 3.6 Concentrations of target compounds at Slough sewage treatment work in 
(ng/l) (2nd sampling)……………………………………………………….……………….….44 
Table 3.7 APCI+ method validation for target compounds…………………………………….45 
Table 3.8 Limit of quantification for each chemical in ng/l………………………………….. 50 
Table 3.9 Blanks data for progestogens……………………………………………………………….51 
Table 3.10 Blanks data for benzotriazoles……………………………………………………………..51 
Table 3.11  Recovery data for progestogens from MilliQ water………………………………52 
Table 3.12  Recovery data for progestogens from final effluent and GAC effluent……53 
Table 3.13 Recovery data for benzotriazoles. ………………………………………….……………54 
Table 3.14 Sampling volume of each sampling point in the STW. ……………………...……57 
Table 3.15 Grid references of the sampling point along the River Erewash. ……………58 
Table 3.16 River Erewash sewage treatment works and calculated per capita effluent 
loads. …………………………………………………………………………………………………65 
Table 3.17 Summary of per capita loads (µg/day) calculated from effluent data from 
STWs on the River Erewash. ……………………………………………………………….65 
 
ix 
 
Table 4.1 Operating parameters for sewage treatment works. ……………………………68 
Table 4.2 Sampling regime achieved at the two conventional STWs. ……..…...…..……70 
Table 5.1 Removal efficiencies for BT and TT through three different 
technologies………………………………………………………………………………………..85 
Table 6.1   Main measured parameters throughout the test (n=16) ……………………….88 
Table 6.2 Nominal concentrations for progestogens. …………………………..………………88 
Table 6.3 Degradation percentage and half lives for progestogens. ……………...………92 
Table 7.1 Types of treatments existed in the eight STWs on the River Erewash....….97 
Table 7.2 Concentrations of progestogens (ng/l) discharged from eight STWs 
existing on Erewash River. ………………………………………………..…..……………99 
Table 7.3 Concentrations of progestogens (ng/l) in Erewash River. ……………..……...99  
Table 8.1 Amount of BT and TT present in dishwasher detergent products from UK 
supermarkets (mg per 20g of tablet or powder). …………………………..……118 
Table 9.1  Occurrences of progestogens in the aquatic environment (ng/l) ………...123 
Table 9.2  Occurrences of benzotriazoles in the aquatic environment (μg/l)………..128 
 
 
 
 
 
 
 
 
x 
 
LIST OF FIGURES 
Figure 2.1   Sources and fate of emerging contaminates in the environment showing 
the range of possible inputs and receptors……………………..…………………….10 
Figure 3.1 Gradient program of methanol for progestogens. ………...…………….…...……39 
Figure 3.2  Gradient program of methanol for benzotriazoles. ………………...……....……40 
Figure 3.3 Flow chart for the final analytical method for progestogens. …………..…….46 
Figure 3.4 Ion chromatography for progestogens………..……………..……………..…….........47 
Figure 3.5 Flow chart for the final analytical method for benzotriazoles...………………48 
Figure 3.4 Ion chromatography for benzotriazoles………..……………..……………..…….....49 
Figure 3.7 Flow diagram and sampling points for Hallam Fields (top) and Newthorpe 
STWs…………………….…………………….…………………….…………………….……….…56 
Figure 3.8 Schematic diagram of the sampling points on the River Erewash and its 
brooks. Numbers refer to locations identified in Table 3.15….….……………59 
Figure 3.9 Location of the sampling point for the degradation test, about ≈ 850m 
downstream Maple lodge STW (Google Earth)…………….……………..……..….61 
Figure 4.1  Sewage treatment works, Hallam Fields STW (left) and Newthorpe STW 
(right). …………………….…………………….…………………….……………………………..67 
Figure 4.2 Concentrations of progestogens in ng/l (A. Settled Sewage. B. RGF Feed.  C. 
Final Effluent) of two sewage treatment works. …………………….….…………71 
Figure 4.3  Percentage removal efficiencies of progestogens through the conventional 
treatment works. (1) Hallam Fields STW, (2) Newthorpe STW.  % 
removed during STW,    % Discharged to the surface water.....……….……74 
Figure 4.4 Concentrations of benzotriazole and tolyltriazole in (ng/l)  Hallam Fields 
STW, Newthorpe STW. …………………….…………………….…………………...……75 
Figure 4.5 Fluxes of benzotriazoles through the conventional treatment works in g/d.  
 Settled sewage,  Final effluent. ………………….…………………….……..…...…76 
 
xi 
 
Figure 5.1 Pictures of the advanced technologies at Hallam Fields STW…………...……78 
Figure 5.2 Removal of progestogens by ozone ( Final Effluent (Pre-O3), Post-
O3...............................................................................................................................................80 
Figure 5.3 Removal of progestogens by GAC ( Final Effluent (Pre-GAC), Post-
GAC).…………………….………….………….……………………….……….…………………….81 
Figure 5.4 Removal of progestogens by chlorine dioxide ( Final Effluent (Pre-ClO2),     
Post- ClO2). …………………….…………………….………………….……………….…….82 
Figure 5.5 Removal of benzotriazoles by ozone ( Final Effluent (Pre-O3), Post-
O3)…………………….………...…………….…………………….…………………….……………83 
Figure 5.6 Removal of benzotriazoles by GAC ( Final Effluent (Pre-GAC), Post-
GAC) …………………….…………….…………………….………………………………………. 84 
Figure 5.7 Removal of benzotriazoles by chlorine dioxide ( Final Effluent (Pre-ClO2) 
Post- ClO2). …………………….…………………….…………………….……………………85 
Figure 6.1 Concentration of progesterone throughout the 14 day test. ………………….89 
Figure 6.2 Concentration of norgestrel throughout the 14 day test. …...………………….89 
Figure 6.3 Concentration of cyproterone acetate throughout the 14 day test…………90 
Figure 6.4 Concentrations of BT and TT in each tank throughout the 14 day test           
(            tank 1 and               tank 2) …………………….…………………….…………….93 
Figure 6.5 Fate of benzotriazole and tolyltriazole throughout the 14 day test                                                          
(              BT,              TT). …………………….………………………………………….………94 
Figure 7.1 Final effluent concentration of benzotriazoles from STWs,        BT,       TT, 
sites are shown as location downstream from the source of the river, left 
to right on x-axis in January 2009…...…………………….……………………………101 
Figure 7.2 Graphical representation of the River Erewash showing concentrations in 
ng/l of BT    and TT       increasing downstream from the river 
source……………………….…………………….…………………….………………………...102  
 
xii 
 
Figure 7.3 Final effluent concentration benzotriazoles from STWs,      BT,       TT, sites 
are shown as location downstream from the source of the river, left to 
right on x-axis in October 2009.………….....……….…………………….……………103 
Figure 7.4 Graphical representation of the River Erewash showing concentrations in 
ng/l of BT    and TT    increasing downstream from the river 
source…………………….…………………….………………………………..…………………104 
Figure 7.5 Concentrations of BT along the River Erewash in the two occasions, 
January (      ) and October   (    )...…...…………….…………………………………….105 
Figure 7.6 Concentrations of TT along the River Erewash in the two occasions, 
January    (        ) and October (       ). ……………………..…………………….………106 
Figure 7.7 Model outputs, showing observed (●) and predicted concentrations of BT 
along the river. Modelled values were calculated using measured effluent 
concentrations (solid line) and per capita loads (dotted line)………….…..107 
Figure 7.8 Model outputs, showing observed (●) and predicted concentrations of TT 
along the river. Modelled values were calculated using measured effluent 
concentrations (solid line) and per capita loads (dotted line). ………….…108 
Figure 7.9 Model outputs for the River Trent catchment scale concentrations of 
benzotriazole and tolyltriazole (ng/l). …………………….……………………...….110 
Figure 7.10 Model outputs for the River Thames catchment scale concentrations of 
benzotriazole and tolyltriazole (ng/l). …………………….………………...……….111 
Figure 8.1 Box plots of concentrations of BT and TT in tap water. Median 
concentrations and the 25-75 percentile range are shown in the box with 
whiskers at 5 and 95 percentiles. …………………….…………………….……….…114 
Figure 8.2 Change in concentration of BT (     ) and TT (     ) in tap water from 13 of 20 
sampling points, error bars show maximum and minimum 
concentration…..…………………….…………………….…………………….…………..…115
 
xiii 
 
LIST OF ABBREVIATIONS, UNITS AND SYMBOLS 
AOP Advanced oxidation process 
APs Alkylphenols 
APCI Atmospheric pressure chemical ionization 
ASP Activated sludge process 
BNR Biological nutrient removal 
BOD Biochemical oxygen demand 
BT Benzotriazole 
CAD Collision gas pressure 
CEH Centre for Ecology and Hydrology 
Ceff Concentration of the effluent  
Cl2O2 Chlorate 
ClO2– Chlorite 
ClO2 Chlorine dioxide 
CPA Cyproterone acetate  
COD Chemical oxygen demand 
CUR Curtain gas 
DBPs Disinfectant by products 
DCM Dichloromethane 
DDT Dichlorodiphenyltrichloroethane 
DES Diethylstilbestrol  
DHG Dydrogesterone 
DSP Drosprinone  
DO Dissolved oxygen 
DOC Dissolved organic carbon 
DP Declustering potential  
DWF Dry weather flow 
E1 Estrone 
E3 Estriol 
EBCT Empty bed contact time 
EE2 17α-ethinyl estradiol 
EDCs Endocrine disrupting chemicals 
 
xiv 
 
EP Entrance potential 
ESI Electrospray ionisation 
F/M Food to microorganism ratio  
FE Final effluent 
FP Focusing potential  
GAC Granular activated carbon 
GC Gas chromatography 
GC/MS Gas chromatography mass spectrometry 
GC/MS/MS Gas chromatography tandem mass spectrometry 
GPC Gel permeation chromatography 
Hc Henery’s law constant 
HgCl2 Mercury chloride 
HLB Hydrophilic-lipophilic balance 
HPLC High performance liquid chromatography 
HRT Hydraulic retention time 
Ka Dissociation coefficient 
Kbiol Degradation constant 
Kd Distribution coeficient 
Kow  Octanol-water partition coefficient 
Ktot. Over all degradation rate 
LC Liquid chromatography 
LC/MS Liquid chromatography mass spectrometry 
LC/MS/MS Liquid chromatography tandem mass spectrometry 
LOD Limit of detection 
LOEC Lowest observed effect concentration 
Log Kow  Logarithm of octanol-water partition coefficient 
LOQ Limit of quantification 
MCRT Mean cell residence time  
MDP Medroxyprogesterone 
MPA Medroxyprogesterone acetate 
MRM Multiple Reaction Monitoring 
MTA Megestrel acetate  
MTBE Methyl tert-butyl ether 
 
xv 
 
MeOH Methanol 
N2  Nitrogen 
N.D Not detected 
NEB Nebulizer gas 
NGL Norgestrel 
NOEC No observed effect concentration 
NTD Norethindrone 
N/AS Nitrifying activated sludge 
O3 Ozone 
PAC Powdered activated carbon 
PAHs Polycyclic aromatic hydrocarbons 
PE Population equivalent 
PGT progesterone 
PPCPs Pharmacetical and personal care products 
POPs presistant organic pollutants 
Q  Volumetric flow rate (m3/d) 
RSD Relative standard deviation 
RO Reverse Osmosis 
RT Retention time 
SPE Solid phase extraction 
SRT Sludge retention time 
STWs Sewage treatment works 
T  Temperature 
TBL Tibolone 
TF Trickling filter 
TT Tolyltriazole 
UK United Kingdom 
USA United State of America 
USEPA United States Environment Protection Agency 
V Volt 
 
xvi 
 
LIST OF PUBLICATIONS 
 
Hussein Janna, Mark D. Scrimshaw, Richard J. Williams, John Churchley & John P. 
Sumpter. (2011) "From Dishwasher to Tap? Xenobiotic Substances Benzotriazole 
and Tolyltriazole in the Environment", Environ. Sci. Technol, vol. 45, no. 9, pp. 
3858-3864.  
 
 
 
 
 
 
 
 
 
 
 
 
Chapter One:  Introduction 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                 Chapter One 
 
2 
 
1.1 Introduction 
One of the most essential components for the existence of life is water. As a result of the 
large increase in the population in the world, there is also an increasing demand for 
clean, safe water which either comes from the fresh water or as a result of reusing 
wastewater directly or indirectly. Therefore, the quality of the water plays a major role 
in the protection of wildlife and human health. 
For many decades, heavy metals and persistent organic pollutants (POPs) were the area 
of interest for most of the researchers in the aquatic environment. However, these 
pollutants have had less awareness when a significant reduction in producing these 
chemicals was achieved and also when “new” or “emerging” unregulated contaminants 
emerged with some environmental problems (Barceló & Petrovic, 2008). 
 The U.S Geological survey  defines emerging contaminants (ECs) as “any synthetic or 
naturally occurring chemical or any micro-organism that is not commonly monitored in 
the environment but has a potential to enter the environment and cause known or 
suspected adverse ecological or human health effects” (USGS, 2011). In addition, Wong 
(2006) has defined ECs as “chemicals (including veterinary and human 
pharmaceuticals) that currently are being used and released into the environment and 
are of special concern due to widespread occurrence and potential for toxic effects”.  
The concern about the presence of these compounds in the environment has led to the 
publication of complete editions of journals dedicated to the topic. For example, 
Environmental Science and Technology published a special issue in December 2006 
about ECs (volume 40, issue 23), followed by Analytical and Bioanalytical Chemistry in 
February 2007 (volume387, issue 4) due the increased interest in the subject. 
There is a large number of ECs in the environment with a myriad of sources and 
pathways. The USEPA have reported in August 2000 that about 87,000 chemicals need 
to be tested to determine if they have endocrine disrupter effects (USEPA, 2000). There 
are about 38,000 chemicals and some heavy metals that are reported as chemical 
substances suspected to have an endocrine disrupting action (Quan et al., 2005). 
Emerging contaminants are released to the environment in different ways. There are a 
very large number of possible emerging contaminants, from industrial chemicals, 
                                                                                                                                                                 Chapter One 
 
3 
 
antiseptic and anti microbial agents, flame retardants, detergents and their derivatives, 
and plasticizers and their derivatives, to the category known as pharmaceuticals and 
personal care products (PPCPs), which are a diverse group of chemicals used in 
veterinary medicine, agricultural practices, human health and cosmetic care (e.g., 
cosmetics, cleaning products, and fragrances). Pharmaceuticals and personal-care 
products (PPCPs) have caught the scientific and public attention and therefore have 
seen a substantial increase in research over the past 10 years above the other emerging 
contaminants (Glassmeyer et al., 2008). 
The presence of emerging contaminants in the aquatic environment represents a 
potential concern to wildlife (Daughton & Ternes, 1999; Pillard et al., 2001; Ferrari et al., 
2003; Barceló & Kettrup, 2004) and they may also have an impact on human health 
(Daughton & Ternes, 1999; Barceló & Petrovic, 2008). Conversely, other scientists think 
that the risks from these substances to human health are negligible (Christensen, 1998; 
Fent, Weston & Caminada, 2006). 
Although much has been published, there still remain gaps in understanding about the 
fate and effect of emerging contaminants in the environment. However, emerging 
contaminants are a wide range of substances, have many different sources and 
pathways, and may have a variety of effects on aquatic organisms and human health.  
In order to identify compounds for inclusion in this study, we have used criteria based 
on biological activity and “new” or “emerging” contaminants which may be present in 
appreciable (µg/l) concentrations. It is also necessary to limit numbers (of chemicals) to 
ensure any work programme is deliverable. Therefore, two groups of compounds, 
progestogens and the benzotriazoles, which have relevance in terms of occurrence, 
removal processes and ecotoxicological effects, have been selected for study.  
 
 
 
 
 
 
                                                                                                                                                                 Chapter One 
 
4 
 
1.2 Aims and objectives 
The overall aim of this study is to understand the occurrence and fate of progestogens 
and benzotriazoles with a focus on the effectiveness of conventional and advanced 
wastewater treatment techniques. This aim will be achieved by determining the 
occurrence of these chemicals in wastewaters and the aquatic environment in the UK. 
Therefore the overall aim of this study will be met through achieving the following 
specific objectives: 
 
1.2.1 To determine the concentrations and removal efficiency of progestogens and 
benzotriazoles in conventional wastewater treatment with different 
biological treatment processes (activated sludge process and trickling filter). 
 
1.2.2 To determine the concentrations and removal efficiency of progestogens and 
benzotriazoles during advanced wastewater treatment (ozone, granular 
activated carbon, and chlorine dioxide). 
 
1.2.3 To determine the degradation rates and fate of progestogens and 
benzotriazoles in surface waters. 
 
1.2.4 Analyse effluent samples from eight further wastewater treatment plants and 
specific points on the river to generate information on spatial distribution. 
Predict the wider occurrence of the progestogens and benzotriazoles in the 
UK by modelling the rivers at a catchment scale. 
 
1.2.5 Analyse drinking water samples to find the concentration of benzotriazoles 
and also analyse different brands of detergents to justify the occurrence of 
these chemicals in the drinking water. 
 
 
 
 
 
 
                                                                                                                                                                 Chapter One 
 
5 
 
1.3 Thesis outline 
 
This thesis is organized sequentially to address the above objectives, therefore chapter 
two provides a review to the available literature regarding the sources and possible 
pathways of emerging contaminants in the aquatic environment. In addition, an 
overview to the removal mechanisms, sewage treatment works and environmental 
impact of these contaminants will also conducted in this chapter. 
One class of steroid hormones, the progestogens, represented by one natural hormone 
and nine synthetic compounds, were selected for this study due to their biological 
activity. Moreover, another group of chemicals, benzotriazoles, which are classified as 
emerging contaminants due to their extensive use in a range of products, represented by 
two compounds, were also chosen for this study. The physicochemical properties of all 
these compounds are illustrated in the Materials and Methods (chapter three), as are 
analytical methods to determine the concentrations of these compounds. In addition, a 
field study, the sampling regimes and quality control, are described in this chapter, along 
with conditions of the degradation study and also the software for modelling. 
The concentrations and removal efficiencies of these 12 compounds in two different 
types of biological treatment, the activated sludge process (ASP) and trickling filter (TF) 
during wastewater treatment works are illustrated in chapter four. Chapter five 
presents the concentrations of these compounds and their removal efficiencies during 
advanced treatment with ozone (O3), granular activated carbon (GAC) and chlorine 
dioxide (ClO2). 
Chapter six describes the behaviour and degradation of these 12 compounds during a 
laboratory test. Monitoring these compounds along the River Erewash with inputs from 
the existing sewage treatment works is also described, along with modelling the 
catchments of the Rivers Trent and Thames in chapter seven. 
 Chapter eight describes the occurrence of the benzotriazoles in drinking water and also 
investigated one of the possible sources of these contaminants. A discussion of the 
results and efforts from this study is undertaken in chapter nine, explaining the possible 
reasons for these results and comparing these results what other people has done. 
Finally a summarization of the total results and major conclusions from these efforts 
about what was achieved in this study were described in chapter 10. 
 
 
 
 
 
 
 
Chapter Two:  Literature Review 
 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                 Chapter Two 
 
7 
 
Overview 
During doing this research, a comprehensive review to the literature has been done in 
order to cover the emerging contaminants in sewage and aquatic environment.  This 
chapter will talk about the history of emerging contaminants in the environment, and 
then discuss the possible sources of these compounds and their pathways to enter the 
aquatic environment. Usage of some chemicals with a high production volume (HPV) 
and also using pharmaceuticals in UK also will be described. An overview of sewage 
treatment works (STWs) and their role to remove these compounds in relation to the 
possible removal mechanisms which may occur will be also covered. Finally advanced 
treatment, represented by current technologies and their ability to remove emerging 
contaminants from effluents will be covered. 
 
2.1 Introduction 
In the environment, emerging contaminants (ECs) are substances released from 
domestic, industrial, and agricultural sources (Yan et al., 2010). These chemicals are not 
routinely monitored but some of them are observed by researchers throughout our 
environment, these substances may have the ability to cause adverse affects in the 
environment (Sumpter & Jobling, 1995; Jobling et al., 1995; Witte, 1998). Emerging 
contaminants have been observed in the aquatic environment in wastewaters, surface 
waters, ground waters, and in some cases in the drinking water (Cancilla, Martinez & 
Van Aggelen, 1998; Stumpf et al., 1999; Ternes et al., 1999; Barnes et al., 2004; Bolong et 
al., 2009; Pojana, Fantinati & Marcomini, 2011).  A wide spectrum of these ECs, both 
natural and synthetic chemicals, have the ability to mimic the natural hormones in the 
body, and may consequently interfere with the endocrine system or interact with the 
hormone receptor and activate or block a response and then could create an adverse 
influence in the body via affecting the reproductive, immune and neurological systems 
(Birkett & Lester, 2003; NIEHS, 2011). Such chemicals are known as endocrine 
disrupting chemicals (EDCs). The issue caught awareness when the environmental 
impacts of some of the ECs were linked with some effects like feminization of fish 
(Desbrow et al., 1998; Jobling et al., 1998), however, for many other substances, their 
                                                                                                                                                                 Chapter Two 
 
8 
 
fate, behaviour, and eco-toxicological impact are still not understood. Conventional 
sewage treatment works cannot remove ECs completely from wastewater although 
these substances undergo different removal mechanisms during the STW processes 
based on their physicochemical properties and (bio) degradability. Advanced treatment 
is a promising technology to remove some of these contaminants, however, each 
technology has advantages and disadvantages in addition to cost/benefit criteria and 
energy consumption of operating these system. In general, ECs represent a challenge to 
the engineers, scientists, and also to society. 
 
2.2 The history of emerging contaminants in the aquatic 
environment 
During the past two decades, there was an increasing concern about the occurrences of 
emerging contaminants in the aquatic environment. However, one of the earliest 
preliminary reports about steroid hormones in wastewater was published in 1965 
(Stumm-Zollinger & Fair, 1965). Then, other researchers published several studies 
about the presence of human hormones and pharmaceuticals in the aquatic 
environment between 1970s and 1980s (Tabak & Bunch, 1970; Hignite & Azarnoff, 
1977; Aherne, English & Marks, 1985). In 1990s, it was feasible to detect these chemicals 
as the technology became more developed, and more attention to the issue began to be 
received from the environmental scientists when some studies linked the presence of 
these chemicals to those released to the environment from the STWs to a toxicological 
impact in aquatic organisms (Desbrow et al., 1998; Jobling et al., 1998; Kramer et al., 
1998; Snyder et al., 2001). During the late 1990s and the past decade, there was an 
abundance of studies which have shown a spectrum of many emerging contaminants 
and their metabolites in the aquatic environment such as  surface waters (Cancilla, 
Martinez & Van Aggelen, 1998; Stumpf et al., 1999; Kolpin et al., 2002; Metcalfe et al., 
2003; Wiegel et al., 2004) , in ground water (Holm et al., 1995; Heberer, Schmidt-
Baumler & Stan, 1998; Peterson, Davis & Orndorff, 2000; Sacher et al., 2001; Barnes et 
al., 2004), and in drinking water ( Boyd et al., 2003; Loraine & Pettigrove, 2006; Kuster 
et al., 2008; Kleywegt et al., 2011; Pojana, Fantinati & Marcomini, 2011). 
                                                                                                                                                                 Chapter Two 
 
9 
 
2.3 Emerging contaminants in the aquatic environment. 
2.3.1 Classification of contaminants. 
There are different types of environmental contaminants and these types are classified 
according to different criteria. Some of these classifications are according to their origin, 
environmental persistence, human toxicity and ecotoxicity. It is possible to say that 
there are three main types of emerging contaminants: 
 Persistent organics: this group represents one of the major groups of emerging 
contaminants in the environment. These are often semi-volatile, halogenated 
compounds used as pesticides or other industrial compounds like flame 
retardants, and pesticide such as DDT. Some of these compounds are still 
produced and in large volumes therefore are classified as high production 
volume chemicals (USEPA, 2011). 
 Pharmaceuticals and personal care products: this group includes all 
pharmaceuticals like antibiotics, antiseptics, anti-inflammatories, and 
antiepileptic drugs. Personal care products include UV protection screens and 
musks. Synthetic hormones such as 17αethinyletsradiol (EE2) are also part of 
this family. 
 Inorganics: this group includes heavy metals like lead, mercury, and arsenic. 
Each group of these three classes has some chemicals that have an impact on the 
endocrine system, therefore some of these chemical are named EDCs. Some of the 
pharmaceutical compounds are biologically active and can affect environmental and 
human health. Because of these interpretations between these chemical in their 
characteristics and then in their impact on human and wild life, it is possible to say 
that these contaminants can belong to more than one group according to the criteria 
of classification. Emerging contaminants may be in any other group, but they are 
emerging only once we become aware of them. 
 
 
 
                                                                                                                                                                 Chapter Two 
 
10 
 
2.3.2 Sources and pathways of emerging contaminants. 
Emerging contaminants are released into the environment via different sources; Figure 
2.1 shows the possible ways of releasing these contaminants. 
Adapted from Nikolaou, Meric & Fatta, 2007 
Figure 2.1 Sources and fate of emerging contaminates in the environment 
showing the range of possible inputs and receptors. 
There are many different sources of ECs into the environment because of the variety in 
the classes of the ECs. Emerging contaminants can be divided into natural and synthetic 
compounds. The natural compounds which are hormones are excreted by vertebrates 
and by some other invertebrates groups (Oehlmann & Schulte-Oehlmann, 2003), while 
synthetic compounds or man-made compounds can be produced by manufacture. 
Factories and manufacture are the main sources of these contaminants where ECs are 
either every day products or used as raw materials to produce other products 
(Marttinen, Kettunen & Rintala, 2003; Moon et al., 2007).  Effluents are discharged from 
these manufacture, for example the pharmaceuticals and personal care products 
industry, mining, rubber manufacturing, corrosion inhibitors and also from pesticides 
industry, although these discharges are mostly controlled by legislation, for example 
IPPC directive (EUROPA, 2011). Therefore, different chemicals were found in the 
                                                                                                                                                                 Chapter Two 
 
11 
 
wastewater like flame retardants (Peng et al., 2009), alkyphenols (APs) and polycyclic 
aromatic hydrocarbons (PAHs) (Vogelsang et al., 2006; Loos et al., 2007), phthalates 
(Balabanic & Klemencic, 2011) and pesticides (Kahle et al., 2008). 
Wastewater treatment plants are also a well known source. Many natural and synthetic 
emerging contaminants from households, hospitals, industrial use, and sometimes from 
storm water enter the sewage treatment works. Because these contaminants are not 
fully or partially removed during the chemical, physical, and biological treatment 
processes (Jones, Voulvoulis & Lester, 2005; Sarmah et al., 2006; Nakada et al., 2006; 
Jones, Voulvoulis & Lester, 2007; Koh et al., 2008; Bolong et al., 2009), a considerable 
amount of these ECs, like natural hormones and benzotriazoles, are released to the 
receiving water (Desbrow et al., 1998; Weiss & Reemtsma, 2005). In addition, in some 
cases (such as storm events), the untreated or partially treated wastewater may reach 
the receiving water and could also have significant amounts of these contaminants. 
Thus, wastewater treatment plants seem to be an important source of emerging 
contaminants (Tan et al., 2007). 
Another possible source for emerging contaminants to enter into the environment is 
storm water runoff. Many types of ECs were found in storm water samples, such as 
flame retardants, plasticizers, pesticides, PPCPs, and heavy metals (Hurst & Sheahan, 
2003). Miltner et al. (1989) found that many emerging contaminants in the influent of 
three STWs came from storm runoff. Boyd et al. (2004) presented results about the 
occurrences of PPCPs and endocrine disrupters in three sites of storm water samples. 
The runoff from the agricultural area is also a source of emerging contaminants 
especially with pesticides to improve crop productivity, antibiotic from animal feed 
process, steroids hormones and antimicrobial from animals and livestock (Birkett, 2003; 
Matthiessen et al., 2006; Song et al., 2007; Snow et al., 2010).  Emerging contaminants 
released from agriculture practices contribute to loading the aquatic environment such 
as antibiotics and hormones as they were detected in a watershed in USA which contains 
62% of the area as an agriculture land (Arikan, Rice & Codling, 2008). Hormones were 
also found in the soil and runoff grasslands in the USA (Finlay-Moore, Hartel & Cabrera, 
2000). In addition fields irrigated with treated wastewater also contribute to provide 
many emerging contaminants and their metabolites to the receiving waters (Pedersen, 
Yeager & Suffet, 2003). The reuse of the wastewater for agricultural purposes may 
                                                                                                                                                                 Chapter Two 
 
12 
 
transfer some of these ECs to the land again, therefore, an environmental and hazards 
risk assessment studies have achieved to evaluate the effect of these ECs and also 
developing the tools or approaches to assess their impact (Dominguez-Chicas & 
Scrimshaw, 2010; Gros et al., 2010). 
The other source is the leakage from landfills, industrial wastes systems, sewer, and 
leakage from sewage treatment facilities. Many different ECs such as pharmaceuticals, 
plasticizers, and pesticides were found in the seepage and leakage water from waste 
landfill (Schwarzbauer et al., 2002). Due to the leakage in the sewage pipes in Germany, 
iodinated contrast x-ray media were found in the groundwater samples (Wolf, Eiswirth 
& Hotzl, 2006). Percolating the rainwater through the domestic landfill and leakage from 
septic tanks are also classified as one of ECs sources (Birkett, 2003).  
 
2.3.3 Analytical methods to determine emerging contaminants 
in aquatic environment. 
After the technology has become more developed to detect trace chemical in the 
aqueous phase, many studies have focused on the methods for determination these 
substances in the environment. Different techniques have been applied in order to 
improve the accuracy of detection these compounds and consequently find the actual 
concentrations. 
The first step of analysis is sample preparation and begins from sample filtration after 
collecting the sample, this is especially for wastewater samples because they contain a 
high loading of organic material and suspended particles, and additionally the purpose 
of this step is to protect the subsequent extraction step. The target chemicals (estrogenic 
components) were not retained by the filter material and they were present in the 
dissolved phase of the sample effluent (Desbrow et al., 1998). Also 99% recovery was 
obtained when wastewater samples were spiked with 17β-estradiol, this means that 
sorption of hormones on filter was negligible (Huang & Sedlak, 2001).  
The next step is extraction of the sample which could be achieved by either liquid/liquid 
separation or solid phase extraction (SPE). The type of separation depends on the type 
                                                                                                                                                                 Chapter Two 
 
13 
 
and properties of the target compound and also on the sample matrix. There are two 
commonly used types of SPE, cartridge or disk. Although disks reduce the clogging of 
sample due to their large surface area, however larger amount of solvent are required 
when using disks in order to elute the analyte and that will increase the method 
duration and consequently time taken to concentrate the eluted sample (Gomes, 
Scrimshaw & Lester, 2003). Further clean up might be required to purify the extracts 
from non target chemicals which is known as purification, which can be achieved by 
separating the interested molecular from other molecular masses based on size by using 
gel permeation chromatography prior to their analysis (Ternes et al., 2002). In some 
cases, there is a need to improve the stability and enhance the detectability, of the 
compounds in order to increase the sensitivity during the use of gas chromatography to 
analyse the target compound, which is known as derivatization. Derivatization is 
achieved by using some agents to derivatise the extracted sample; nevertheless, these 
advantages are sometimes offset by loss of sample during the additional manipulation 
(Desbrow et al., 1998; de Alda & Barcelo, 2001). 
There are many different methods to quantify the ECs in the aquatic environment.  
Biological techniques such as immunoassay are among the most sensitive analytical 
techniques; however, they are limited by the availability of the specific antisera and 
subject to cross-reactivity (de Alda & Barcelo, 2001). Other two methods which are 
commonly used for quantification of compound of interest after extraction are gas 
chromatography (GC), and liquid chromatography (LC) coupled to mass spectrometry 
(MS) or tandem mass spectrometry (MS/MS).  Despite the fact that chromatographic 
methods are not as sensitive as biological techniques, however chromatographic 
methods are widely used due to their ability to screen steroids and their conjugate 
simultaneously (de Alda & Barcelo, 2001).   
There are several studies achieved to determine the concentration of many EDCs in the 
aquatic environment using biological techniques (Huang & Sedlak, 2001; Xin et al., 
2009), and chemical methods, for LC/MS/MS (Vanderford et al., 2003; D'Ascenzo et al., 
2003; Voutsa et al., 2006; Gros, Petrovic & Barcelo, 2006; Hernando et al., 2006; Gomez 
et al., 2006; Vega-Morales, Sosa-Ferrera & Santana-Rodriguez, 2010; Sapozhnikova et al., 
2011), for GC/MS   (Daughton & Ternes, 1999; Labadie & Budzinski, 2005a; Labadie & 
Budzinski, 2005b), and for GC/MS/MS (Huang & Sedlak, 2001; Kolodziej, Gray & Sedlak, 
                                                                                                                                                                 Chapter Two 
 
14 
 
2003; Ternes et al., 2003; Kolodziej, Harter & Sedlak, 2004).  Extraction and purification 
were involved in most of these studies in order to quantify the concentrations of target 
compounds.  
GC/MS and GC/MS/MS are unlike LC/MS/MS, in that they are limited to the volatility 
property and molecular weight of the chemical of interest. In addition, LC/MS could 
screen the conjugated and unconjugated chemicals without need from derivatization (de 
Alda & Barcelo, 2001). Several of these methods demonstrated a high limit of detection 
from the wastewater samples compared to the other samples collected from clean river 
or lake water or drinking water and this is due to the matrix of the sewage samples. For 
example, the limit of detection was from 0.3-600 ng/l in the study of steroids in the 
urine and final effluent sample (D'Ascenzo et al., 2003), also from 0.6-35 ng/l during the 
observation of hormones and antibiotic in the influent and effluent wastewater in 
Germany (Schlu sener & Bester, 2005).  
 
2.3.4 The occurrence of emerging contaminants in the aquatic 
environment. 
There are a large number of emerging contaminants that are potentially present in the 
environment. Emerging contaminants include PPCPs, hormones and veterinary 
medicines, household compounds, and some chemicals used in industry. There is a wide 
spectrum of studies from a number of countries focused on these contaminants in terms 
of their occurrence, behaviour in the aquatic environment and also their impact on 
humans and aquatic organisms. Therefore this section will provide a very brief review of 
the literature which demonstrates their presence in wastewaters (influent and effluent), 
river waters, ground waters, and in drinking waters.  
Worldwide, the high usage of chemicals in industry and households, and also the use of 
therapeutic drugs, is likely to make the presence of these substances in the environment 
unavoidable. In addition, unused medicines and the surplus chemicals used for domestic 
use might be discharged through the sewerage system. As a result of leakage from septic 
tanks or throughout the sewer systems, some of these chemicals are then transmitted to 
the ground waters. There are several studies which have reported the occurrence of 
different chemicals in ground waters (Heberer et al., 1997; Sacher et al., 2001; 
                                                                                                                                                                 Chapter Two 
 
15 
 
Schwarzbauer et al., 2002; Drewes et al., 2003; Wolf, Eiswirth & Hotzl, 2006; Vulliet et 
al., 2008; Barnes et al., 2008; Schulz et al., 2008; Silvia Diaz-Cruz & Barcelo, 2008; Teijon 
et al., 2010). 
However, the bulk of contaminants will flow to the STWs and therefore it is very likely to 
find these compounds in the influent of the STWs at concentrations ranging from ng/l to 
μg/l. Due to incomplete removal of ECs in the STWs (Nakada et al., 2006; Koh et al., 
2008; Bolong et al., 2009; Kusk et al., 2011), this means that these contaminants will also 
be present in the effluent of the STWs, and that the residual concentrations will be 
discharged to the receiving water bodies. Many studies have illustrated the occurrence 
of ECs in the wastewater treatment processes (Stumpf et al., 1999; Petrovic et al., 2002; 
Andersen et al., 2003; Joss et al., 2004;  Weiss & Reemtsma, 2005; Carballa, Omil & Lema, 
2005; Carballa et al., 2005; Sarmah et al., 2006; Nakada et al., 2006; Reemtsma et al., 
2006; Voutsa et al., 2006; Choi et al., 2008; Kuster et al., 2008; Chang et al., 2008; 
Reemtsma et al., 2010; Gros et al., 2010; Sodre, Locatelli & Jardim, 2010; Jelic et al., 
2011; Chang et al., 2011; Fan et al., 2011) and also in surface waters (Aherne, English & 
Marks, 1985; Kolpin et al., 2002; Boyd et al., 2003; Moldovan et al., 2007; Nakada et al., 
2007; Vieno et al., 2007; Choi et al., 2008; Kim et al., 2009; Benotti et al., 2009; Jover, 
Matamoros & Bayona, 2009; Chang, Wan & Hu, 2009; Reemtsma et al., 2010). 
Because some of these chemicals are recalcitrant, they will persist in the environment 
and it is also possible that they will be present in the potable water when the surface or 
ground waters are contaminated and used as a drinking water supply ( Aherne, English 
& Marks, 1985; Vieno, Tuhkanen & Kronberg, 2005; Loraine & Pettigrove, 2006; 
Richardson et al., 2007; Kuster et al., 2008; Sodre, Locatelli & Jardim, 2010; Benotti et al., 
2009; Pojana, Fantinati & Marcomini, 2011). 
 
 
2.3.5 The impact of emerging contaminants in the aquatic 
environment. 
In history, for about 33 years since 1938, diethylstilbestrol (DES) was given to avoid 
miscarrying of pregnant women (CDC’s DES Update, 2009). Afterwards, it was revealed 
that DES can alter the fertility and reproductive performance of the children of mothers 
who were directly exposed to this synthetic hormone (CDC’s DES Update, 2009). Due to 
                                                                                                                                                                 Chapter Two 
 
16 
 
the variety in the types of ECs particularly EDCs and each compound has a different 
properties and modes, thus each chemical behaves differently in the environment. 
Although there is a vast number of substances that are released to the environment have 
not been studied yet in terms of their potential effect to the environment, however there 
is a large number of studies demonstrating the effects of the ECs on the environment 
and therefore it would be difficult to cover the impact of studied compounds on the 
environment especially on wildlife and human.  The endocrine system can be affected by 
many natural and synthetic chemicals such as natural and synthetic estrogens, natural 
androgens, pesticides, phthalates, and bisphenol A (Richardson, 2009). Organisms in the 
surface waters are exposed to the contaminants and most of them affected at 
concentrations as low as a few ng/l due to the continuous release of ECs (Daughton & 
Ternes, 1999; Barcelo & Kettrup, 2004).  Some chemicals have the ability to accumulate 
in the fat tissue and cause adverse effect to the organisms, such as the feminization and 
reproductive problems of fish in the surface water due to uncompleted removal of 
estrogens from the STWs (Purdom et al., 1994; Jobling et al., 1998; Kramer et al., 1998). 
The declination in population of bald eagle was correlated with some ECs in Chesapeake 
Bay (Wiemeyer et al., 1984).  Invertebrates can be also influenced by ECs and may be 
more sensitive than vertebrates (Ferrari et al., 2003; Kusk et al., 2011). Humans can be 
exposed to the ECs via the drinking water or food chain and consequently might be 
affected.  Although there are some studies have shown no substantial concern about the 
effect of ECs on human and they are unlikely to harm the human (Christensen, 1998; 
Webb et al., 2003) , however there is a suspicion about declining the number of sperm in 
human due to the impact of ECs even though not confirmed yet (Richardson, 2009). 
In conclusion, the impact of ECs on the environment and wild life represented by some 
problems in reproductive systems in fish, birds, and mammals in addition to the 
breakage of eggs of fish, birds and turtles, additionally feminization of male fish and 
finally  some changes in the immunologic system of marine mammals. The ECs can 
influence the human also represented via reduction in sperm count and increase the 
incidence of breast or endometriosis cancer for women, testis and prostate cancer from 
men (Esplugas et al., 2007). 
 
                                                                                                                                                                 Chapter Two 
 
17 
 
2.4 Overview of STW. 
The main aim of the wastewater treatment works is to produce treated effluent that is 
suitable and safe to discharge to the environment and increasingly to reuse it. Therefore, 
the role of wastewater treatment is to convert the waste material present in the 
wastewater to stable oxidised end products (Gray, 2004). The sewage treatment works 
normally consists of physical, chemical and biological processes in order to remove the 
physical, chemical and biological contaminants. Therefore STWs are assembled from a 
combination of unit processes. In general, there are five stages during sewage treatment 
(Gray, 2004): 
 Preliminary treatment: gross solid and grit are removed and sometime oil and grease 
as well if they present in large amount. 
 Primary (sedimentation) treatment: the settable solids are removed in the 
sedimentation tanks. 
 Secondary (biological) treatment: in this stage, the organic matter (dissolved and 
colloidal) with presence of microorganisms is removed. 
 Tertiary treatment: the residual suspended solid and nutrient are removed. 
 Sludge treatment: sludge collected from previous stage are treated by dewatering, 
stabilization in order to disposal it.  
Many studies have focused on the removal of emerging contaminants (ECs)   during 
secondary treatment (biological treatment). This is because other studies have shown 
that the major removal of these compounds is by biodegradation and adsorption. 
Therefore, this section will focus on the fate and behaviour of these compounds during 
the treatment processes, but mainly during the biological treatment which is usually 
consists of activated sludge process (ASP) or trickling filter (TF). 
 
2.4.1 Preliminary treatment. 
The function of screens, shredders, grit removal, and flow equalization in the head of 
sewage treatment works is to protect the downstream equipments and to provide a 
homogenous feed to subsequent processes facilities (Davis, 2011). Large floating objects 
and small amount of organic matter are removed via screens. Grit and dense material 
                                                                                                                                                                 Chapter Two 
 
18 
 
solids are removed by grit removal. A small amount of emerging contaminants were 
removed during preliminary treatment (Lester & Edge, 2000; Fan et al., 2011). 
 
2.4.2 Primary treatment. 
In this stage, the raw sewage enters the primary sedimentation tanks and in this process 
the settable solids (suspended solids) are removed from wastewater by allowing the 
particles to gravitate to settle in the bottom of the tank. The most significant mechanism 
in primary sedimentation tanks is adsorption onto solids, which is under the impact of 
the gravity settle from the primary sludge. Many factors could affect the degree of 
pollutant removal, one of the important factors is the hydrophobicity of the compound, 
and also suspended solids which is controlled by settling characteristics of the particle 
and also the operation specification of the settling tank such as retention time and 
surface loading rate play an important role (Langford & Lester, 2003; Carballa et al., 
2005). 
 
2.4.3 Secondary treatment. 
In this stage, the settled sewage enters the secondary treatment which is biological 
treatment. The aspect of this process depends on the presence of aerobic bacteria and 
other microorganisms to oxidize or incorporate into cells the organic matter. This 
treatment occurs by providing a sufficient amount of oxygen to the bacteria (Langford & 
Lester, 2003). Trickling filter where the large population of microorganisms are 
attached to the fixed surface and the ASP where the large population of microorganisms 
mix with the wastewater are the two main kinds of biological treatment. Each one of 
them is normally followed by a secondary sedimentation, the purpose of secondary 
sedimentation tank is to separate the dense microbial biomass that formed during the 
biological conversion from the water by settlement (Gray, 2004). 
 
 
                                                                                                                                                                 Chapter Two 
 
19 
 
Activated sludge process (ASP) 
The most common and widely used type of biological treatment at large STW is ASP, 
treating both industrial and domestic wastewater. The name derived from the 
process itself where air is injected to the reactor and biomass is recirculated to the 
aeration tank continuously. The activated sludge system consists of three main 
divisions (Metcalf & Eddy, 2003): 
 Reactor in which the microorganisms are responsible for treatment are kept in 
suspension and aerated. 
 Liquid solid separation system which is sedimentation tank usually. 
 Recycle system which is responsible for feeding solids that settled in the 
sedimentation tank to the aeration tank.  
The performance of activated sludge process to remove estrogens in Brazilian STW was 
better than that of the trickling filter (Ternes et al., 1999). There are many advantages 
and disadvantages for using activated sludge process and these depend on the type of 
the process. For example, the advantages of some types are less space, higher level of 
ammonia removal and odour free. However, the required energy for aeration tank is 
high, and also the flexibility to change the effluent characteristics is limited (Metcalf & 
Eddy, 2003). There are many factors that could affect the process such as the 
characteristics of the wastewater being treated, foaming due to detergents, temperature, 
return rate, and oxygen availability (Gray, 2004).  
 
 Trickling filter (TF) 
Fixed film or attached growth systems, trickling filter, has been used for about 100 years 
(Metcalf & Eddy, 2003). In trickling filter, wastewater is sprinkled over the media 
continuously where the microbial biomass is present as a film which grows on the 
surface of an inert or solid medium (Gray, 2004). The conventional trickling filter using 
circular rock as the packing materials and now days have been converted to plastic 
packing in order to increase the treatment capacity. 
 There are many advantages of using this kind of biological treatment like easy to 
operate, low energy required, less equipment maintenance, and better sludge 
                                                                                                                                                                 Chapter Two 
 
20 
 
thickening. However, the effluent quality from fixed- film system are relatively poorer 
than suspended growth systems in terms of biochemical oxygen demand (BOD) and 
suspended solids (SS) (Metcalf & Eddy, 2003). 
There are many factors that could affect the performance of a trickling filter like 
hydraulic and organic matter, media type and depth, retention time, and temperature 
(Metcalf & Eddy, 2003; Gray, 2004). Therefore, there is a relatively variation in the 
removal efficiency of some ECs like estrogens in trickling filter (Svenson, Allard & Ek, 
2003).  
 
2.5 Removal mechanisms. 
Contaminants undergo to different mechanisms in order to be removed during their 
presence in the sewage. There are different types of removal mechanisms that might 
occur during the sewage treatment which are mainly biodegradation, sorption, 
photolysis and volatilization. The first two types represent the main mechanisms that 
have the potential to remove pollutant from the sewage water (Daughton & Ternes, 
1999; Vader et al., 2000; Ternes et al., 2004; Onesios, Yu & Bouwer, 2009; Chang et al., 
2011). Below is a brief definition of each mechanism.  
 
2.5.1 Biodegradation. 
Biodegradation is one of the most significant removal mechanisms for emerging 
contaminants. One of the main objectives of the biological treatment in the STW is to 
reduce the concentrations of the organic matter. This could be achieved by transform 
the biodegradable constituents into acceptable end product. Another object is also to 
remove the nutrients such as phosphorus and nitrogen. Therefore nitrification and 
denitrification are the main processes that occurred during the biological treatment. The 
biological conversion of ammonia to nitrate is known as nitrification which is technically 
occurred into two steps, where nitrosomonas bacteria oxidize the ammonia to nitrite 
(NO2-N) and nitrobacter bacteria oxidize nitrite to nitrate (NO3-N) (Langford & Lester, 
2003). Many factors can affect the nitrification rate such as dissolved oxygen level, pH, 
                                                                                                                                                                 Chapter Two 
 
21 
 
temperature, metals, acids and free ammonia (Metcalf & Eddy, 2003). However 
nitrification requires a high retention time, low food to microorganism ratio (F/M), and 
high mean cell residence time (MCRT) or sludge age. The integral step to get a suitable 
end product is denitirfication which is a biological reduction of nitrate to nitrogen gas 
(N2) occurred and that achieved by a facultative heterotrophic bacteria that get the 
oxygen either from the dissolved oxygen or from the nitrate molecules. This process of 
denitrification only occurs when the oxygen level are very low (anoxic condition) and 
bacteria use nitrate-oxygen (Gray, 2004). 
Biological degradation occurs in two phases, aerobic degradation and that happen in 
activated sludge, trickling filter, or anaerobiclly in the sewage system or at sludge 
digesters (Langford & Lester, 2003). Halling-Sorensen et al. (1998) reviewed 
pharmaceuticals as emerging contaminants in the environment; they stated that the 
contaminants in the sewage treatment works could undergo one or more of these three 
fates: 
 Mineralization which the substance eventually mineralized to CO2 and H2O. 
 The contaminant may transform to become more hydrophobic and a portion of 
the substance partitions onto the solid portion. 
 Transformation to more hydrophilic persistent compounds, which are discharged 
to the receiving water body. 
An intensive study by Joss et al. (2006) investigated the biodegradation of 35 different 
emerging contaminants like pharmaceuticals, personal care products and hormones. 
According to the degradation constant (Kbiol) value, target compounds were categorised 
into three groups. The first group which included four compounds (hormones and 
pharmaceuticals), more than 90% was transformed when (Kbiol>10/gss/d). Partial 
degradation was achieved when (0.1< Kbiol<10/gss/d), and no degradation was 
observed for 17 compounds (<20% transformed) when Kbiol <0.1/gss/d). In the 
wastewater treatment processes, biodegradation is the main removal mechanism to 
remove progestogens (Fan et al., 2011). 
Emerging contaminants have a wide range of degradation rates and therefore their half 
lives are different. Some of these are biodegraded readily like 17β-estradiol (E2) (Joss et 
al., 2004), or some of them have a half-life for more than 100 days (Benotti & 
                                                                                                                                                                 Chapter Two 
 
22 
 
Brownawell, 2009) , while other compounds are more resistant and not degraded. 
Although many studies have shown the importance of this process, however, little is 
known about the biodegradation of many emerging contaminants and the factors that 
can affect their degradation rate. 
2.5.2 Sorption. 
This is the second of the most significant process that control the fate of emerging 
contaminants in the aquatic environment. It is a physical process where the more 
lipophilic (hydrophobic) contaminants partition onto the settled sewage solids in the 
primary sedimentation tank or to biomass in the biological stage.  Rogers (1996) divided 
the sorption potential for the compounds according to their octanol-water coefficient 
value to: 
 Low sorption potential when Log Kow less than (2.5). 
 Medium sorption potential when log Kow between (2.5-4.0). 
 High sorption potential when log Kow more than (4.0). 
The ratio between the concentrations in the solid and liquid phases at equilibrium 
conditions which is solid-water distribution coefficient (Kd) can also give a good 
prediction for sorption potential  and therefore have become common approach to 
determine the partitioning of ECs, particularly PPCPs (Suarez et al., 2008). According to 
Ternes et al. (2004), there are two sorption mechanisms: 
 Absorption which is hydrophobic interaction of the aliphatic and aromatic groups 
of a compound with the lipophilic cell membrane of the micro-organisms and the 
lipid fractions of the sludge. Therefore, the sorption potential in this phenomenon 
depends on the octanol-water partition coefficient (Kow). 
 
 Adsorption which are electrostatic interactions of positively charged groups of 
chemicals with the negatively charged surfaces of the micro-organisms. In this case 
the dissociation coefficient (Ka) for the compounds plays an important role to 
determine the sorption potential for chemicals. 
In general, therefore, these two coefficients (Kow) and (Ka) are guide to predict the 
sorption potential of emerging contaminants particularly PPCPs. 
                                                                                                                                                                 Chapter Two 
 
23 
 
2.5.3 Photolysis. 
This mechanism may be responsible for complete or partial removal of some ECs. 
Yamamoto et al. (2009)  showed that some emerging contaminants were relatively 
easily photodegraded, while other compounds were relatively stable against sun light. 
There is a wide range of half lives for emerging contaminants, some of these compounds 
were easily photolyzed and some were more slowly to degrade depending on conditions 
(Gomez et al., 2008). Therefore, many factors could affect the removal rate positively or 
negatively such as pH, oxygen concentration, structural properties of the compound, and 
occurrence of organic matter (Lin & Reinhard, 2005; Neamtu & Frimmel, 2006). In 
addition, the STW configuration plays a role in photolysis, for example large aeration 
tanks or polishing lagoons allow for some photolysis to occur (Metcalf & Eddy, 2003). 
 
2.5.4 Volatilization. 
The removal of volatile organic compounds from wastewater surfaces to the atmosphere 
is named volatilization (Metcalf & Eddy, 2003). According to the physiochemal 
properties of the compounds like Henry’s law constant (Hc) and the octanol-water 
partition coefficient (Kow), the volatilisation potential can be predicted (Rogers, 1996): 
 The compound has a low volatilization potential when Hc <1x10-4 and 
(Hc/Kow) <1x10-9. 
 The compound has a high volatilization potential when Hc >1x10-4 and 
(Hc/Kow) >1x10-9. 
Therefore, this mechanism seems to be negligible for most of the emerging 
contaminants especially with compounds that have a hydrophilic behaviour. 
Pharmaceutical compounds and hormones have low Hc and consequently have low 
potential volatilization. Conversely, musk fragrances have Hc and Hc/Kow higher than the 
limit mentioned by Rogers (1996), therefore, a high potential volatilization may be 
expected especially with the aerated biological treatment due to the abundance of air 
(Ternes et al., 2004). 
 
                                                                                                                                                                 Chapter Two 
 
24 
 
2.6 Advanced treatment. 
Many ECs are only partially removed in conventional wastewater treatment (Nakada et 
al., 2006; Kuster et al., 2008; Bolong et al., 2009; Gros et al., 2010; Jelic et al., 2011). Thus, 
one approach to improve the removal efficiency of the STWs for ECs is by adding a 
further technology as one of the alternative solutions. Advanced treatment is defined as 
the additional treatment required to remove suspended, colloidal and dissolved 
substances remaining after conventional secondary treatment (Metcalf & Eddy, 2003). 
There is a wide variety of treatment technologies have been applied and developed. 
Advanced treatment technologies can be classified according to their operation types or 
according to the residual compounds that are required to be removed and some of these 
are micro-and ultra-filtration, reverse osmosis, electro dialysis, adsorption, ion 
exchange, advanced oxidation processes and chemical precipitation ( Metcalf & Eddy, 
2003; Gray, 2004). An overview of some available technologies such as ozone (O3), 
granular activated carbon (GAC), and chlorine dioxide (ClO2) are described below. 
 
2.6.1 Treatment by ozone (O3). 
In order to decrease the concentrations of the organic compounds in the sewage water, 
ozonation and particularly advanced oxidation processes (AOPs), therefore, are used 
(Metcalf & Eddy, 2003). Ozone is an extremely reactive oxidant; unstable and 
decomposed to oxygen quickly after generation, therefore it must be generated onsite. 
Ultraviolet (UV) irradiation of air or oxygen and corona discharge are used to generate 
O3 (Gomes & Lester, 2003). Many studies have shown that ozonation is a very effective 
technique to decrease the concentrations or remove some hormones and PPCPs from 
wastewater (Ternes et al., 2003; Jasim et al., 2006; Esplugas et al., 2007; Zhang, Yamada 
& Tsuno, 2008; Gagnon et al., 2008; Giri et al., 2010;).  For specific ECs like bisphenol-A, 
nonylphenol, and also 17-β estradiol, ozonation was found very useful to reduce the 
concentrations of these chemicals and their estrogenicity in secondary effluents (Kim et 
al., 2008). In addition, the removal efficiency of estrogens could be affected by pH, since 
the removal efficiency at pH 3 has been observed to be higher than that one at pH 11 
                                                                                                                                                                 Chapter Two 
 
25 
 
(Maniero, Bila & Dezotti, 2008), although changing the pH of sewage may not be 
practical. 
A study by Huber et al. (2005a), presented that ozone could oxidize more than 90% of 
PPCPs and estrogens in wastewater samples at a dose of 3.5 mg/l. Similar results were 
achieved by Hashimoto, Takahashi & Murakami (2006), showing that ozonation with 
1mg/l could remove more than 90% of estrogens, and to below the limit of detection for 
estrogens when the ozone dose was increased to 3 mg/l.  Another study by Ternes et al. 
(2003), found that in municipal STW in Germany that by applying 10-15mg/l of O3 and 
18 minutes as a contact time, it was able to decrease the concentration of 
pharmaceutical compounds, hormones and musk fragrances in his study to be below the 
limit of detection. However other compounds like iodinated contrast media were still 
detected with that level of ozone dose. There was a correlation between the dose of O3 
applied and the removal efficiency to remove some estrogenic compounds in bench 
scale for effluent from STW in Denmark (Hansen, Andersen & Ledin, 2010). Additionally 
to ozone dose, contact time also plays an important role in removing ECs as it can be 
seen in the study achieved to remove nonylphenol (NP) and bisphenol (BPA) from 
wastewater in Italy, hence 30% of NP were removed during 15 minutes at a dose of 8 
mg/l and about 60% were removed at the same dose with 30 minutes (Bertanza et al., 
2010). As a result, many factors could affect the performance of the ozonation such as 
ozone dose, contact time, the characteristics of the target compounds and the 
wastewater, pH, and temperature (Yargeau & Leclair, 2008). 
These studies have shown an evidence of the role of ozone in removing wide spectrum 
of ECs in pilot and full scale experiments in both water and wastewater treatment 
plants. However, there are some drawbacks in using this technology such as the 
formation of disinfection by products (DBPs). Because of the O3 dose applied in the 
wastewater treatment is higher than the dose in drinking water treatment, therefore, 
that will lead to generate more DBPs in wastewater effluent than in the drinking water 
(Wert et al., 2007). Many types of DBPs like aldehydes (formaldehyde, acetaldehyde, 
glyoaxl, and methyl glyoxal), various acids (acetic acid, formic acid, oxalic acid, and 
succinic acid) and ketones are formed during ozonation in the absence of bromide, while 
other DBPs may also generated in the presence of bromide such as bromated ion, 
bromoform, and brominated acetic acid and in some occasion hydrogen peroxide is also 
                                                                                                                                                                 Chapter Two 
 
26 
 
produced (Metcalf & Eddy, 2003). A direct relationship was found between the dose of 
O3 applied to remove pharmaceuticals and bromide ion concentration as DBPs (Kim & 
Tanaka, 2010).  
In general, ozone is very powerful oxidant and ozonation is the most studied oxidation 
processes with best expectations; the performance of ozonation is a function of some 
parameters like dose, contact time, and properties of the substances present in the 
aqueous phase.  
 
2.6.2 Treatment by chlorine dioxide (ClO2). 
Due to the variability in the performance of the conventional STWs in eliminating 
emerging contaminants (Koh et al., 2008), therefore there may be a need to improve the 
removal efficiency and that can be achieved by installing additional treatment. Chlorine 
dioxide is one of these additional technologies to enhance the effluent quality, it is 
powerful oxidant that oxidises the organic compounds presented in water, it unstable, 
therefore it has to be generated onsite (Metcalf & Eddy, 2003). Because of many 
pharmaceuticals have phenolic moieties and /or amino group in their structure, thus a 
large number of these pharmaceuticals are expected to be oxidised with ClO2 (Huber et 
al., 2005b; Lee & von Gunten, 2010).  
 There are a few studies focused on the performance of ClO2 in the aquatic environment, 
for example (Huber et al., 2005b; Filby et al., 2010). However the study by Huber et al 
(2005b) demonstrated that ClO2 was effective to remove some classes of emerging 
contaminants like antibiotics and estrogens although it reacts more slowly than ozone 
with these compounds in water treatment samples. Another study showed that ClO2 is 
highly effective to oxidize the estrogens (more than 90% removal) with the wastewater 
samples (Filby et al., 2010). 
 Although it is a very effective oxidant it also produces residuals, however, and one of the 
main disadvantages of using this technology is formation of disinfection by products 
(DBPs), the principle DBPs formed are chlorite (ClO2–) and chlorate (Cl2O2) which are 
potentially toxic (Metcalf & Eddy, 2003). Additionally, ClO2 decompose in sunlight, is 
highly corrosive and moderately expensive (Metcalf & Eddy, 2003). 
                                                                                                                                                                 Chapter Two 
 
27 
 
2.6.3 Treatment by granular activated carbon (GAC). 
 Activated carbon is another effective technology used to eliminate a wide spectrum of 
contaminants. Initially, activated carbon was used to remove taste and odour from 
drinking water. Nowadays it has been used in the sewage treatment and water works in 
order to remove the organic pollutants. There are two types of activated carbon that are 
usually used in the advanced treatment, powder activated carbon (PAC) and granular 
(GAC) are widely used. A number of studies have reported the performance of these 
processes to remove contaminants from the aqueous phase (Filby et al., 2010; Zhang & 
Zhou, 2005; Kim et al., 2007). Pojana, Fantinati & Marcomini (2011) found GAC was 
more efficient than other technologies (ozone treatment & sand filtration) in his study to 
remove pharmaceutical compounds in drinking water treatment plants. However, PAC 
were tested to remove EDCs like 17α-ethynylestradiol and 17β-estradiol from raw 
drinking water and achieved a range of removal efficiency from 31-99% based on many 
parameters like type of PAC, dose of PAC and the presence of organic materials in the 
water, it also paralleled to the physiochemical properties of the EDCs particularly log 
Kow, where the high removal correspond to the high log Kow (Yoon et al., 2003). In 
addition, in an extensive study by Westerhoff et al. (2005)  to understand the fate of 
endocrine disrupters in simulated drinking water treatment process, showed that 
adding 5mg/l of PAC with four hours of contact time could remove between 10 to >98% 
of the compounds depending on their physicochemical properties, and it also 
demonstrated that a high dose (20 mg/l) of PAC at the same contact time (4 hours) 
enhanced the EDCs removal to more than 90%. Therefore the dose of the PAC and the 
contact time may play an important role in the removal efficiency. 
The effectiveness of GAC as an adsorbent was shown in the removal of 17α-
ethynylestradiol from wastewater by sand, GAC, and manganese oxide (de Rudder et al., 
2004),  where the results demonstrated removal efficiencies were 17.3% by sand, 99.8% 
by GAC, and 81.7% by manganese oxide. In another study (Ifelebuegu et al., 2006), the 
removal efficiency of 17α-ethynylestradiol from wastewater by coal based GAC was 
98.6%, by coconut based GAC  99.3%, and  by wood based GAC 96.4%. This shows that 
the source of GAC may have some influence on removal efficiency. Therefore, activated 
carbon is a successful technology to remove emerging contaminants from aqueous 
                                                                                                                                                                 Chapter Two 
 
28 
 
phase (Chang et al., 2009); however, there are some disadvantages such as saturation of 
the GAC which then requires regeneration. 
In general, among these advanced treatments, the main principle of GAC is to remove 
ECs from the aqueous phase depending on adsorption removal mechanism, while the 
function of O3 and ClO2 treatment is to oxidise or transform these ECs depending on the 
chemical oxidation, but not remove them and consequently that may create, 
transformation products or new compounds (DBPs) which may have an adverse effect 
on the environment. It also been noticed that a series or combination of these 
technologies provides a significant control to remove contaminants from wastewater 
(Gray, 2004). 
 
2.7 Selection of emerging contaminants in this study. 
There is a large number of emerging contaminants are released to the environment. 
However limited information is available about ECs in terms of their occurrence, fate, 
and toxicity associated to the humans and wildlife. Pharmaceuticals and personal care 
products (PPCPs) is a group of large number of compounds, and they are widely used in 
society. This group includes many different types such as hormones (natural and 
synthetic), drugs (antibiotic, anti-epileptics), and musk fragrances.  There are adverse 
effects on the aquatic and wild life when these compounds are released to the 
environment due to their bioactivity (Jobling et al., 1998; Barcelo & Kettrup, 2004). 
There is large number of steroid hormones and each group of hormones consists of a 
range of compounds with different properties, therefore it is necessary to choose a 
particular group for this investigation. Progestogens (natural and synthetic) are one 
group of steroid hormones of emerging contaminants, represented by progesterone 
(natural hormone) and nine other synthetic compounds were chosen in this study.  
Nowadays many chemicals are extensively used in the industry, some of these chemicals 
are persistent, and could have an impact on humans and wildlife by disrupt the 
endocrine system due to their accumulation and bioactivity. One of these chemicals 
group is benzotriazoles which are produced in large amount and therefore are classified 
as HPV according to USEPA (USEPA, 2011). Thus, benzotriazole and tolyltriazole were 
                                                                                                                                                                 Chapter Two 
 
29 
 
also selected in this study.  Because of the limited information available for some of the 
selected compound in these two groups, therefore, a brief description about selected 
groups in this study are described below. 
 
2.7.1 Progestogens. 
Many of the hormonally-active micropollutants known to date, and of most concern, are 
steroids, or steroid-like molecules. Some of these, in particular synthetic compounds 
such as ethynyl estradiol (EE2), used in the contraceptive pill, are relatively resistant to 
biodegradation, and cross the gills of fish very readily, where they interact with specific 
receptors and/or enzymes to disrupt the endocrinology of the fish. These chemicals can 
cause adverse effects even when present in the aquatic environment at extremely low 
(sub ng/l) concentrations. So, based on that knowledge, it is likely that there are other 
classes of hormonally-active synthetic steroids, besides EE2, in the aquatic environment 
that could cause adverse effects. One obvious group would be the synthetic 
progestogens, which are the other active ingredient of many contraceptives (at doses 
higher than EE2) and are also used in hormone replacement therapy (Bromley, de Vries 
& Farmer, 2004). Endogenous (natural) progesterones play important roles in 
reproduction in fish, controlling maturation of the gametes (sperm and oocytes) in both 
sexes. Synthetic progestogens target the progesterone receptor in women, and as fish 
also have this receptor, so it seems likely that synthetic progestogens will target these 
receptors. All of this information suggests that synthetic progestogens may have effects 
on fish reproduction and the key issue is really at what concentration do synthetic 
progestogens cause adverse effects, and how different is this concentration to those in 
the aquatic environment (Sumpter, 2008). There is some evidence that natural 
progesterone and synthetic progestogens are present in wastewaters in Europe (Vulliet 
et al., 2007) and that advanced treatment, such as ozonation will effectively remove 
progesterone (Snyder et al., 2006). However, there is no comparison of removal in such 
advanced treatment processes with what may be achieved in biological processes, and in 
particular, evidence that nitrifying bacteria enhance removal rates of other hormonally 
active compounds with similar structures, such as the steroid estrogens (Vader et al., 
2000; Leusch et al., 2005; Ren et al., 2007).  
                                                                                                                                                                 Chapter Two 
 
30 
 
Ten compounds were selected as a part of the compounds in this study to represent the 
progestogens group and the selection was based on the amounts prescribed in 2006 in 
the United Kingdom for clinical use. In total, 1,700kg of progestogens were used, while 
estrogens and androgens were only 500kg and 300kg respectively (Runnalls et al., 
2010). These compounds are cyproterone acetate, drosprinone, dydrogesterone, 
medroxyprogesterone, medroxyprogesterone acetate, megestrel acetate, norethindrone, 
norgestrel, progesterone, and tibolone.  
 
2.7.2 Benzotriazoles. 
Benzotriazole (1H-benzotriazole) and tolytriazole (4 or 5-methyl-1H-benzotriazole) are 
commonly used domestic and industrial chemicals (Voutsa et al., 2006; Giger, Schaffner 
& Kohler, 2006). Despite this, surprisingly little is known about the environmental 
contamination of surface waters by these compounds or, indeed, about any chronic 
toxicity that may result from the exposure of aquatic organisms to this chemical. The 
compounds are anticorrosive agents, making up between 10-20% of formulated aircraft 
deicing and antifreeze fluids, of which 8,000,000 litres are used per year in Canada alone 
(Cancilla et al., 1997). For this reason, much of the attention on environmental 
concentrations has focused on runoff from airports, as well as on the water bodies and 
groundwater systems receiving such runoff (Cancilla, Martinez & Van Aggelen, 1998; 
Corsi et al., 2003). However, benzotriazole is also used in machine dishwashing 
detergents for silver protection (Ort et al., 2005). Within the UK, dishwasher ownership 
has risen from less than 5% in 1977 to over 33% in 2006 (Waterwise, 2011). Recent 
studies have demonstrated that benzotriazole exhibits antiestrogenic activity in vitro, 
although this was not observed in vivo (Harris et al., 2007), although a wider range of 
tests would be required to be certain that this was generally true. Nonetheless, 
benzotriazole has been described as ‘‘toxic to aquatic organisms and can cause long-
term adverse effects in the aquatic environment’’ (Hem & Weideborg, 1999). These 
compounds are therefore considered to represent chemicals with a range of uses, likely 
to be present in relatively high concentrations which exhibit low removal and hence 
have been selected for study. 
 
 
 
 
 
 
 
 
 
 
 
 
 
Chapter Three:  Materials, Methods, and Field Study 
Description 
 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                             Chapter Three 
 
32 
 
Overview 
To date, various methods have been developed and introduced to measure emerging 
contaminants. However, quantification of low concentrations is one of the main 
challenges in the analysis of these contaminants (Petrovic, Gonzalez & Barcelo, 2003). 
This chapter will describe the experimental methods used in this work including 
reagents, chemical standards, and analytical procedure. In addition, it will describe the 
field study sites including the STWs, River Erewash and catchment, and tap water survey 
area sampling procedure. Moreover, modelling the River Erewash and its catchment and 
Thames catchment area and the method to calculate the concentrations of 
benzotriazoles for wider area are also described in this chapter. Furthermore, the 
validation of the methods used to determine the benzotriazoles and progestogens is also 
described. 
3.1 Experimental method. 
3.1.1 Reagents and chemical 
 
3.1.1.1 Analysed standards 
The purity of all analyzed standards was greater than 98%. Cyproterone–acetate (CPA), 
megetsrel–acetate (MTA), medroxyprogesterone (MDP), and progesterone (PGT) were 
purchased from QMx, (Essex, UK). Norethindrone (NTD), drosprinone (DSP), 
dydrogesterone (DHG), norgestrel (NGL), tibolone (TBL), and medroxyprogesterone–
acetate (MPA) were obtained from LGC (Exeter, UK). Benzotriazole (BT) and 
tolyltriazole (TT) were purchased from Sigma-Aldrich (Gillingham, UK). Table 3.1 shows 
the full description of each chemical. 
 
3.1.1.2 Internal standards 
Deuterated norethindrone and progesterone with a greater than 98% chemical purity 
were obtained from QMx and Aldrich respectively. These internal standards were used 
to quantify the progestogens group.  The internal standard 5, 6-dimethylbenzotriazole 
was used to quantify the benzotriazoles group and was also purchased from Sigma- 
Aldrich (Gillingham, UK). Table 3.1 also summarizes the details of the internal standards. 
                                                                                                                                                             Chapter Three 
 
33 
 
3.1.1.3 Solvents and standard solutions 
Organic solvents were of HPLC grade: methanol, dichloromethane and methyl tertiary 
butyl ether MTBE were purchased from Rathburn Chemicals (Walkerburn, UK). Nitric 
acid was purchased from Fisher (Loughborough, UK) and then diluted to 3%. Stock 
solutions were prepared in methanol.  For solid phase extraction, Oasis HLB 
(500mg/6cm3) cartridges were obtained from Waters Ltd. (Watford, UK). The other 
three types of cartridges which are C18CC, C18EC, and Easy were obtained from Thames 
Restek Ltd. (Saunderton, UK). Reagent grade MilliQ water (18.2MΩ) (Millipore, Watford, 
UK) was used for blanks, spiked and preparation of solutions. For HPLC analysis an 
Ascentis c18 (10cm x 2.1mm) 2.7μm column from (Sigma, Gillingham, UK) was used to 
separate progestogens, and a Synergi 4μ Hydro-RP80A column from (Phenomenex, 
Macclesfield, UK) was used for  benzotriazole separation, and both were protected by 
using a C18 Guard column. The standards used in the method were prepared by further 
dilution of the stock standards with methanol/ water (50:50v/v). 
3.1.2 Reference standards preparation. 
3.1.2.1 Progestogens 
A standard stock solution of 0.1 g of each compound was dissolved into a 100 ml 
volumetric flask of HPLC grade methanol. Around 1000 µg/ml individual stock solution 
of each compound (deuterated and non-deuterated) were prepared in methanol. A 
series of mixed calibration standards containing all ten analytes in MeOH/H2O (50/50), 
at a concentration range 0.5-500 ng/ml, and deuterated internal standards at  100 
ng/ml were prepared from the stock solution. 
3.1.2.2 Benzotriazoles 
Standard solutions were prepared from individual stock solutions. About 0.1 g of each 
compound was dissolved into 100 ml of HPLC grade methanol in order to get 1,000 
µg/ml. A series of mixed calibration standards containing analytes to produce six- point 
calibration at a concentration range 2.5 – 5,000 ng/ml and the internal standard (100 
ng/ml) in methanol/water (50/50) were prepared, along with a solution of 
benzotriazole and tolyltriazole at 1000 ng/ml for use in spiking samples to evaluate 
method recovery and performance. A solution of internal standard was prepared in 
methanol at 10 µg/ml for addition to samples prior to extraction. 
                                                                                                                                                                                                                                                                   Chapter Three 
 
34 
 
Table 3.1 Details of selected progestogens and benzotriazoles. 
Compounds abbr. CAS Formula Log Kow a Systematic  Name b Structure c 
Cyproterone acetate CPA 427-51-0 C24H29ClO4 3.87(±0.55) 
H-Cyclopropa 
(1,2)pregna-1,4,6-triene-
3,20-dione, 17-
(acetyloxy)-6- 
chloro-1,2-dihydro-, 
(1beta,2beta) 
 
Drospirenone DSP 67392-87-4 C24H30O3 3.59(±0.68) 
6-beta,7-beta;15-beta,16-
beta-Dimethylene-3-oxo-
17-alpha-pregn-4-ene-
21,17-carbolactone 
 
Dydrogesterone DHG 152-62-5 C21H28O2 3.56(±0.31) 9-beta,10-alpha-Pregna-4,6-diene-3,20-dione 
 
Medroxyprogesterone MDP 520-85-4 C22H32O3 3.42(±0.13) 
Pregn-4-ene-3,20-dione, 
17-hydroxy-6-methyl-, 
(6-alpha)- (9CI)  
 
a: created from (ALOGPS 2.1)(VCCLAB, 2011)   b, c: adapted from (U.S. NLM, 2010)  
 
                                                                                                                                                                                                                                                                   Chapter Three 
 
35 
 
Table 3.1 Continued 
Compounds abbr. CAS Formula Log Kow a Systematic  Name b Structure c 
Medroxyprogesterone 
acetate MPA 71-58-9 C24H34O4 3.63(±0.32) 
Pregn-4-ene-3,20-dione, 
17-hydroxy-6alpha-
methyl-, acetate (8CI)  
 
Megestrel acetate MTA 595-33-5 C24H32O4 3.78(±0.37) 
17-Hydroxy-6-
methylpregna-4,6-diene-
3,20-dione 17-acetate  
 
Norethindrone NTD 68-22-4 C20H26O2 3.29(±0.47) 
19-Nor-17alpha-pregn-4-
en-20-yn-3-one, 17-
hydroxy- (8CI)  
 
*Norethindrone d6   52-78-8 C20H20O2D6   19-norethindrone-2,2,4,6,6,10-d6   
Norgestrel NGL 6533-00-2 C21H28O2 3.66(±0.44) 
18,19-Dinor-17-alpha-
pregn-4-en-20-yn-3-one, 
13-ethyl-17-hydroxy-, (+-)- 
 
 
                                                                                                                                                                                                                                                                   Chapter Three 
 
36 
 
Table 3.1 Continued 
Compounds abbr. CAS Formula Log Kow a Systematic  Name b Structure c 
Progesterone PGT 57-83-0 C21H30O2 3.77(±0.19) Pregn-4-ene-3,20-dione 
 
*Progesterone d9   15775-74-3 C21H21O2D9   progesterone-2,2,4,6,6,17α,21,21,21-d9   
Tibolone TBL 5630-53-5 C21H28O2 3.4(±0.62) 
19-Norpregn-5(10)-en-
20-yn-3-one, 17-hydroxy-
7-methyl-
, (7alpha,17alpha)- 
 
Benzotriazole BT 95-14-7 C6H5N3 1.24(±0.18) 1,2,3-Benzotriazole 
      
Tolyltriazole TT 136-85-6 C7H7N3 1.59(±0.23) 1H-Benzotriazole, 4(or 5)-methyl- 
 
* 5,6-
dimethylbenzotriazole   4184-79-6 C8H9N3   
5,6-Dimethyl-1H-
benzotriazole 
  
*: (internal standards) adapted from (ChemicalBook, 2008) 
                                                                                                                                                             Chapter Three 
 
37 
 
3.1.3 Instrumentation  
Both LC/ESI+ /MS/MS and LC/APCI+/MS/MS system were used to perform the analyses. 
The system consisted of an HPLC (Hewlett Packard 1050) coupled to a Perkin Elmer 
Series  200 auto sampler and a PESciex API 365  triple quadruple mass spectrometer 
with atmospheric pressure chemical ionization (APCI) in positive mode in order to 
determine the concentration of progestogens. An electro spray ionization source (ESI) in 
positive mode was used to determine the concentrations of benzotriazoles. Acquisition 
and evaluation of data, in addition to instrument control, were carried out by Analyst 
software 1.4.2 (Applied Biosystems, Warrington, UK).  
 
3.1.3.1 LC/MS/MS method 
In order to get the maximum sensitivity for the chemicals of interest, the two modes ESI 
and APCI were selected and tuned by experiments. A 250μl syringe was installed on 
syringe pump. The flow rate for each individual standard that was infused by the syringe 
pump was 50 µl/min. The positive mode produced more parent ions than the negative 
mode and was then optimized in order to get higher sensitivity. The main parameters 
for the instrument to improve the signal intensity for chemicals were optimized as 
below: 
 Temperature (T) = 300 °C.  
 Nebulizer gas (NEB) = 6. 
 Curtain gas (CUR) = 8. 
 Collision gas pressure (CAD) = 4. 
 Focussing potential (FP) = 115 V. 
 Declustering potential (DP) = 15 V. 
 Entrance potential (EP) = 4 V.   
An HPLC method to separate the compounds was then developed. Table 3.2 shows the 
retention time and the masses for each compound. 
 
 
 
 
 
                                                                                                                                                             Chapter Three 
 
38 
 
Table 3.2 Retention time and masses for progestogens. 
Compound Retention time (min.) M1 M2 
1 Cyproterone acetate  29.22 417.2 313.2 
2 Drosprinone  27.24 367.2 97.1 
3 Dydrogesterone  29.11 313.2 145.2 
4 Medroxyprogesterone  29.34 345.1 123.1 
5 Medroxyprogesterone acetate  29.84 387.1 123.1 
6 Megestrel acetate  29.57 385.3 267.2 
7 Norethindrone  26.70 299.2 109.2 
8 Norethindrone d6  26.70 305.4 113.3 
9 Norgestrel  28.27 313.4 109.2 
10 Progesterone  30.05 315.1 97.1 
11 Progesterone d9  30.05 324.3 100.2 
12 Tibolone  28.25 313.2 145.2 
 
For benzotriazoles, multiple reaction monitoring (MRM) was used with parent and 
fragment ions shown in Table 3.3. Two fragment ions were used for the determinants, 
one for quantification and the second for confirmation. Tolyltriazole (4(or 5)-methyl-
1H-benzotriazole) consists of two isomers, the 4- and 5-methyl, however these were not 
separated by the chromatography, and are reported together as tolyltriazole 
Table 3.3 Retention time and masses for benzotriazoles. 
Compound Retention time (min) [M+H+] Quantification ion Confirmation ion 
1 Benzotriazole 2.03 120.1 65.1 92.2 
2 Tolyltriazole 3.17 134.2 79.1 95.1 
3 5,6-dimethylbenzotriazole 5.04 148.2 93.1 * 
* Single ion used for the internal standard 
 
 
 
                                                                                                                                                             Chapter Three 
 
39 
 
3.1.3.2 Chromatography. 
Progestogens 
The concentration of analytes were determined using LC (APCI+)/MS/MS at a flow rate 
of 0.2 ml/min. Analytes were separated using an Ascentis c18 (10cm x 2.1mm) 2.7μm 
column, (Sigma, Gillingham, UK). The total run time was 45 minutes, with data 
acquisition over a methanol/water (+0.4% formic acid) gradient of: 5% MeOH for 2 
minutes, linear gradient to 80% MeOH over 25 minutes and held at 80% for 5 minutes, 
followed by a column wash for 1 minute and equilibration back to starting conditions for 
13 minutes for a 46 minute cycle time as shown in Figure 3.1. The mass spectrometer 
was operated in a positive APCI mode using multiple reactions monitoring (MRM). 
 
Figure 3.1 Gradient program of methanol for progestogens. 
Benzotriazoles 
Benzotriazole and tolyltriazole were quantified using a LC (ESI+)/MS/MS system. 
Analytes were separated on a 7 cm x 2 mm i.d. Synergi 4μ Hydro-RP80A column 
(Phenomenex, Macclesfield, UK) at a flow rate of 0.2 ml/min with an initial mobile phase 
of 55% water and 45% methanol (both solvents with 0.4% formic acid). This was 
increased to 70% methanol / formic acid over four minutes, and held for a further four 
minutes before returning to initial conditions for the next sample as shown in the Figure 
                                                                                                                                                             Chapter Three 
 
40 
 
3.2. Instrument control, integration and quantification of samples were undertaken 
using the Analyst software.  
 
Figure 3.2 Gradient program of methanol for benzotriazoles. 
 
3.1.4 Development of an analytical method for progestogens 
One of the main important parts in the evaluating the occurrence of trace chemicals in 
the environment is the analytical method. However, much effort was involved in 
developing and validating these techniques. Examine different cartridges to obtain the 
best recovery was one of the attempts in order to develop the method. Trying to 
optimize the source parameters for the mass spectrometer was also one of the attempts. 
In addition to that, using gel permeation chromatography (GPC) cleanup was also one of 
the attempts to improve the analytical method by separating the big fragments from the 
fragments of the chemicals of interest. The purpose of all these efforts was to increase 
the accuracy for detection and determination the concentrations of these chemicals in 
the aquatic samples. 
                                                                                                                                                             Chapter Three 
 
41 
 
3.1.4.1 Cartridges types 
During the period of developing the method, four different types of cartridges were 
examined. The purpose of this test was to assess the efficiency of these cartridges via 
finding the recovery for these compounds from these cartridges. Therefore, duplicate 
samples (each sample 1l of pure water 18 MΩ) were spiked with 100 ng, extracted and 
then analysed by LC/MS/MS for each type of cartridges. The results showed that C18cc 
provided the largest set of the mean recovery compared to the other cartridges, 
however HLB cartridges were chosen due to two reasons: firstly, there was no 
significant difference between C18cc and HLB mean recovery, and secondly Vulliet et al. 
(2007), recommended to use HLB cartridges in the analytical method for determination 
selected steroid sex hormones in wastewater. Table 3.4 shows the recovery percentage 
with each type of cartridges.  
Table 3.4 Mean recovery percentage of progestogens from different cartridges. 
 Cartridge type 
Compound  C18EC HLB C18CC Easy 
Drospirenone 53 72 78 35 
Dydrogesterone 51 59 69 38 
Medroxyprogesterone 54 79 78 51 
Medroxyprogesterone acetate 41 62 61 33 
Norethindrone 98 88 92 93 
Norgestrel 53 87 81 49 
Progesterone 42 62 64 38 
Tibolone 60 80 83 51 
 
 
3.1.4.2 Slough data and validation 
Base line data 
The first sampling was undertaken to detect these compounds from wastewater sample 
from Slough STW to the west of London was on 13 of September 2008. The purpose of 
this sampling was to investigate the presence or the background concentrations of the 
12 emerging contaminants (10 progestogens, and two benzotriazoles) in wastewater 
sample associated with our study and also to inform us of how much we have to spike at 
appropriate levels for the next stage. Electrospray Ionization in positive (ESI+) mode 
with LC/MS/MS was used to analyse these compounds. At that time, triplicate samples 
                                                                                                                                                             Chapter Three 
 
42 
 
(1 litre each) was taken from a bulk samples of 5 l collected from each crude and final 
effluent. The extraction of samples by SPE was within 5 hours of sampling. 
Concentrations of these compounds were in low ng/l for progestogens and two orders of 
magnitude higher for BT and TT as shown in Table 3.5. 
Table 3.5 Concentrations of target compounds at Slough sewage treatment 
work in (ng/l) (1st sampling). 
 Compounds  
Sample 
name CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL BT TT 
Crude 1 39.6 13.2 18.8 22.2 11.0 7.2 15.5 27.4 30.2 38.8 2500 910 
Crude 2 38.2 11.9 11.8 19.2 10.3 4.9 10.5 17.8 30.2 31.6 3180 1270 
Crude 3 18.2 14.4 10.8 24.2 10.0 5.7 15.3 29.8 39.6 46.4 3330 1360 
Mean 32.0 13.2 13.8 21.9 10.4 5.9 13.8 25.0 33.3 38.9 3000 1180 
RSD % 37 9 32 11 5 20 21 25 16 19 15 20 
FE 1 5.4 6.5 6.0 10.4 10.6 6.5 5.4 14.4 6.8 22.8 3450 2470 
FE 2 5.6 6.6 9.0 6.0 8.5 1.4 4.1 12.6 5.6 23.0 3750 2530 
FE 3 9.2 4.8 5.4 5.1 10.2 2.8 2.9 45.0 6.3 69.8 3360 2440 
Mean 6.7 6.0 6.8 7.1 9.7 3.6 4.1 24.0 6.2 38.5 3530 2480 
RSD % 32 17 28 40 11 73 30 76 10 70 6 2 
 
All ten compounds in this study were found in the crude and final effluent samples. In 
addition, initial indications were that there was limited removal for some of these 
chemicals during the conventional process.  
Method evaluation 
The next sampling was on 23 of September from the STW that sampled previously. The 
purpose of this sampling was to validate the method by spiking at relevant 
concentration to detect these pollutants in wastewater sample. Electrospray ionization 
(ESI+) in positive mode with LC/MS/MS was used to analyse these compounds. 
For progestogens, samples were collected from crude and final effluent in 10 l and 20 l 
containers respectively. The crude samples were divided into ten samples, each sample 
was 0.5l, the first five samples were not spiked (no progestogens added), while the 
second five samples were spiked with 20 ng of progestogens to validate the method and 
to find out the recovery percent of the samples. For the final effluent, samples were 
categorised into three groups and each group consists of five samples with 1l each and 
                                                                                                                                                             Chapter Three 
 
43 
 
measured as unspike samples, spike samples with 5 ng, and spike with 10 ng of 
progestogens.  
Benzotriazoles had the same procedure as progestogens except the volume of the 
sample was 200 ml and spiked with 500 ng of benzotriazoles in both crude and final 
effluent samples to determine the method validity and the recovery percentage of the 
samples.  
From the results in Table 3.6, it is clear to see that all compounds were present also in 
the influent and final effluent samples of the wastewater; also the recovery for the high 
spike volume in the final effluent samples was more accurate than in low spike volume. 
 
                                                                                                                                                                                                                                                                   Chapter Three 
 
44 
 
 
 
Table 3.6 Concentrations of target compounds at Slough sewage treatment work in (ng/l) (2nd sampling). 
 
  Compounds 
    CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL BT TT 
Crude sewage unspiked: sample 
volume is 0.5l for progestogens 
and 0.2l for benzotriazoles 
Mean (ng/ sample Vol.) 14.4 5.2 12.6 5.3 4.5 4.5 4.1 7.7 10.8 11.9 553 667 
% RSD 40 23 20 32 10 12 24 26 8 20 1 2 
Crude spiked at 20 ng of 
progestogens samples and 500ng 
of benzotriazoles samples 
Mean (ng/ sample Vol.) 39.5 11.0 7.4 32.0 13.9 11.2 12.8 25.8 29.4 34.1 964 1092 
% RSD 36 60 51 62 31 28 8 65 14 43 4 6 
% Mean recovery 126 29 -26 129 47 33 42 112 93 82 84 86 
Final effluent unspiked: sample 
volume is 1l for progestogens 
and 0.2l for benzotriazoles 
Mean (ng/ sample Vol.) 8.1 4.7 8.3 6.8 4.3 4.0 1.7 5.8 4.2 9.7 314 487 
% RSD 68 44 28 119 96 90 71 90 106 78 4 6 
Final effluent spiked at 5 ng for 
progestogens samples   
Mean (ng/ sample Vol.) 7.9 6.0 5.9 13.2 9.4 9.8 5.7 12.4 7.6 18.1   
% RSD 62 10 52 13 18 15 21 62 23 61   
% Mean recovery -4 27 -49 125 104 114 79 163 68 124   
Final effluent spiked at 10 ng for 
progestogens samples and 500 
for  benzotriazoles samples 
Mean (ng/ sample Vol.) 10.0 11.6 12.6 18.0 11.3 7.7 10.4 13.8 11.1 23.4 921 1284 
% RSD 27 21 32 33 22 23 40 41 35 36 6 5 
% Mean recovery 20 69 43 109 71 36 86 100 69 101 101 118 
                                                                                                                                                             Chapter Three 
  
45 
 
3.1.4.3 Problem with and solution to progestogens analysis 
Different limitations had occurred during development the method for analysing 
progestogens, especially with GPC, since the first sample set of data were very good 
compared to the later data set. Many problems had occurred with GPC such as the auto 
sampler did not communicate with the collector, therefore, that led to loss many 
samples. Changing the auto sampler to new one had made many problems specifically 
with the pressure. All these factors led to investigating a change from using the ESI+ to 
APCI+. Vanderford et al. (2003) used both ESI+ and APCI+ in analysing progesterone; 
therefore, the decision to investigate the method performance by using APCI+ was made. 
To validate the method, a bulk samples of 15 litres was collected from Cranfield 
University STW in order to validate the method and check the method performance, 
therefore, the bulk sample was divided into three groups: the first group consisted of 
five samples each one was one litre as unspiked samples, five samples each one was 1l 
were spiked at 5ng represented the second group, and third group of five sample also 
each sample was one litre with 10ng spiked. Table 3.7 shows the method validation by 
using APCI+ at two different levels of spiking. The mean recovery in both levels was very 
good (72%-129%), therefore, APCI+ source was used to analyse the progestogens in this 
study, because it is less sensitive to suppression so it does not require cleanup. 
Table 3.7 APCI+ method validation for target compounds.  
Compound 
 CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Final effluent 
unspiked (n=5) 
 
Mean (ng/ l) 1.4 1.7 0.5 0.4 3.3 0.6 0.5 3.6 0.7 0.6 
%RSD 34 29 55 67 50 43 53 20 13 70 
Final effluent spiked 
at 5 ng/l (n=5) 
  
   
Mean (ng/ l) 6.1 8.1 4.8 5.6 6.9 6.9 4.5 8.0 4.6 5.4 
% Mean recovery 95 129 84 100 72 125 78 110 78 72 
%RSD 9 45 12 7 37 10 15 36 11 16 
Final effluent spiked 
at 10 ng/l (n=5) 
    
Mean (ng/ l) 13.1 12.2 11.0 11.0 13.4 11.3 9.0 13.0 8.8 11.3 
% Mean recovery 117 106 105 103 101 105 83 116 80 79 
%RSD 11 12 34 7 36 9 4 26 9 27 
 
                                                                                                                                                             Chapter Three 
  
46 
 
3.1.5 Final analytical methods 
3.1.5.1 Analytical method for progestogens  
The final analytical methods of progestogens followed the method of Vanderford et al. 
(2003). Wastewater samples were filtered by GF/C (0.45μ) (Whatman, Maidstone, UK) 
filters. Internal standard (0.2 ml of 100 ng/ml) was then added to the sample. Cartridges 
were preconditioned with 5ml of methanol, followed by 5ml of reagent grade 18MΩ 
water before loading the sample with a flow rate between 5-10 ml/min using a vacuum 
manifold. After extraction, the cartridges were rinsed with 5ml of reagent water and 
dried with a stream of air for about 3hours. Cartridges were then eluted with 5 ml (90% 
of MTBE, 10% MeOH) followed by 5 ml of MeOH. These elutes were collected in 15 ml 
polypropylene tubes, and were subsequently evaporated on a miVac concentrator 
(Genevac, USA) at 35 °C on the [-OH] programme setting for 65 minutes and then 
evaporated to dryness with nitrogen. Samples were reconstituted with 0.2 ml of MeOH / 
H2O (50:50 v/v) into 800μl small vials and transferred to auto an sampler prior to 
quantification by LC(APCI+)/MS/MS. Figure 3.3 shows the systematic arrow diagram for 
the final analytical method for progestogens. 
 
Figure 3.3 Flow chart for the final analytical method for progestogens. 
 
                                                                                                                                                             Chapter Three 
  
47 
 
The ion chromatography for the progestogens resulted from following this analytical 
method for one sample from final effluent is shown in Figure 3.4. The numbers in the 
graph refer to the each single compound as they listed in Table3.2. 
 
Figure 3.4 Ion chromatography for progestogens 
 
3.1.5.2 Analytical methods for benzotriazoles 
Samples of wastewaters, river waters and tap waters were enriched by SPE before 
quantification. Figure 3.5 shows the flow chart for the final analytical method for 
analysing benzotriazoles, which was based on that of Vousta et al. (2006). Before 
extraction, samples were filtered by GF/C filter paper, acidified to pH <3 with diluted 
nitric acid (3 %) (Fisher, Loughborough, UK) and internal standard (0.2 ml or 1 ml of 
100 ng/ml in methanol, depending on the final volume that samples would be made up 
                                                                                                                                                             Chapter Three 
  
48 
 
to) was added. The Oasis cartridges were prepared by washing with 5 ml of methanol 
followed by 5 ml of reagent grade water. Samples were loaded onto the cartridges using 
a vacuum manifold at a flow rate of 5 to 10 ml/min. For wastewaters and river waters, a 
sample volume of 200 ml was used and 1000 ml for tap waters. After the extraction, the 
cartridges were rinsed with 5 ml of reagent water and dried with stream of air. 
Cartridges were then eluted with 5 ml of dichloromethane (DCM) with 3% methanol. 
These elutes were subsequently concentrated on a miVac concentrator (Genevac, 
Ipswich, UK) at 35 °C on the [-OH] programme setting for 45 minutes. They were then 
evaporated to dryness with a stream of nitrogen and re-dissolved in 0.2 ml or 1ml of 
methanol / water (50:50), depending on the required concentration factor needed, prior 
to quantification by LC (ESI+)/MS/MS.  
 
 
Figure 3.5 Flow chart for the final analytical method for benzotriazoles. 
 
                                                                                                                                                             Chapter Three 
  
49 
 
The total ion chromatogram (TIC) for the benzotriazoles resulted from following this 
analytical method for a typical sample is shown in Figure 3.6.  
 
 
 
Figure 3.6 Ion chromatography for benzotriazoles. 
 
3.1.6 Quality  control 
3.1.6.1 Limit of detection (LOD) and limit of quantification (LOQ) 
The minimum concentration or amount of analyte that can be reliably distinguished is 
defined as the limit of detection (Taverniers, De Loose & Van Bockstaele, 2004). While 
the limits of quantification can be defined as the minimum concentration can be 
quantified in the sample which has the compound of interest. In this study the detection 
limit was calculated at least three times the signal to noise and limit of quantification 
was taken as 2 times the LOD according to (Taverniers, De Loose & Van Bockstaele, 
2004). Table 3.8 shows the limit of quantification for the compounds of interest. 
 
BT TT 
5, 6-dimethylbenzotriazole 
                                                                                                                                                             Chapter Three 
  
50 
 
Table 3.8 Limit of quantification for each chemical in ng/l.  
 
   Compounds 
Progestogens Sample CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
 Final Effluent & Post 
Advanced treatment (1l) 0.2 1 1.6 0.4 0.4 0.4 1 2 0.4 1.6 
 Settled Sewage (0.5l) 0.4 2 3.2 0.8 0.8 0.8 2 4 0.8 3.2 
 
Benzotriazoles Sample BT TT         
 Tap Water (1l) 0.5 0.5         
 Settled Sewage, Final 
Effluent & Rivers (0.2l) 2.5 2.5         
 Post advanced treatment 
(0.1l)  5 5         
 
3.1.6.2 Blanks 
Progestogens 
To find out whether there was any contamination had occurred during sample 
preparation, extraction and analysis, at least one sample of 1l of non-spiked MilliQ water 
was analysed in each batch. Then, the value of the contamination was subtracted from 
the samples. For progestogens, Table 3.9 represents the data of the blank samples for 
the chemicals of interest and these samples were achieved during collecting and 
analysing the samples from STWs and during the degradation study. It is obvious to see 
that the blanks in the degradation study are better than the blanks that were done on 
site and that probably because of the quality of the MilliQ water in the both locations and 
also possibly more difficult to ensure a good washing for glassware on-site. 
Benzotriazoles 
Table 3.10 represents the blank data for benzotriazoles of all sample batches that 
achieved during the study which means from sewage treatment works (Slough, Hallam 
Fields and Newthorpe STWs), the Erewash River, the degradation study and the tap 
water in addition to some laboratory samples. 
 
 
 
                                                                                                                                                             Chapter Three 
  
51 
 
Table 3.9 Blanks data for progestogens. 
 
Sample Name CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Slough STW Blank 1  < 0.2  < 1 4.2 0.7  < 0.4  < 0.4  < 1 < 2  < 0.4 2.6 Blank 2  < 0.2  < 1 4.3 0.9  < 0.4 0.3  < 1 < 2  < 0.4  < 1.6 
Hallam 
Fields & 
Newthorpe 
STWs 
Blank1 1.3  < 1 3.3  < 0.4  < 0.4  < 0.4  < 1 < 2  < 0.4  < 1.6 
Blank2 1.4  < 1 4.8 1.2 1.3  < 0.4  < 1 < 2  < 0.4 1.6 
Blank3 5.3 7.1 20.4 6.7 5.2 2.1 2.5 6.2 5.7 9.7 
Blank4 1.7 4.9 8.0 4.1 2.8 1.3 1.8 2.8 3.2 3.6 
Mean 2.4 3.1 9.1 3.0 2.3 0.9 1.2 2.5 2.3 3.8 
RSD % 80 110 85 98 94 109 94 108 119 108 
Degradation 
Study 
Blank1 2.3 4.3 1.8 0.6 5.7  < 0.4  < 1 3.3  < 0.4  < 1.6 
Blank2 2.2 4.1 3.8 2.8 2.0 2.9 1.8 8.0 0.8 6.2 
Blank3 1.0 4.0 1.8 0.4 2.8 0.3  < 1 1.6 0.5 2.1 
Blank4  < 0.2  < 1  < 1.6 1.3  < 0.4  < 0.4  < 1 < 2  < 0.4  < 1.6 
Mean 1.4 3.2 2.0 1.3 2.7 0.8 0.7 3.4 0.4 2.3 
RSD % 75 62 72 83 88 163 111 99 90 120 
 
Table 3.10 Blanks data for benzotriazoles. 
Sample Name  BT ng/l  TT ng/l 
Slough STW Blank (1) < 0.5 < 0.5 Blank (2) < 0.5 < 0.5 
Hallam Fields  
&  
Newthorpe STWs 
Blank (1) < 0.5 4.0 
Blank (2) < 0.5 < 0.5 
Blank (3) < 0.5 < 0.5 
Blank (4) < 0.5 < 0.5 
Erewash River Blank (1) < 0.5 < 0.5 Blank (2) 1.0 2.0 
Degradation Study Blank (1) < 0.5 < 0.5 Blank (2) 2.4 3.0 
Tap water 
Blank (1) 1.5 0.8 
Blank (2) 0.9 0.6 
Blank (3) < 0.5 < 0.5 
Blank (4) 1.1 < 0.5 
Blank (5) < 0.5 < 0.5 
Blank (6) 1.6 < 0.5 
Blank (7) 1.7 0.6 
Blank (8) 1.8 0.7 
Laboratory  Test Blank (1) < 0.5 < 0.5 Blank (2) 0.9 < 0.5 
Mean 0.8 0.8 
                                                                                                                                                             Chapter Three 
  
52 
 
3.1.6.3  Recoveries. 
Progestogens 
One litre of MilliQ water and wastewater samples were spiked at different 
concentrations with each batch in order to determine the method performance. 
Recovery wastewater samples were selected from different stages through the whole 
processes, while MilliQ water samples was spiked. Blank samples were also subtracted 
from the spiked sample. Spiked samples were extracted at the same time of each batch. 
Table 3.11 shows the recovery percentage of these chemicals from spiked MilliQ water 
in the two different stages of the study. The mean recovery from the degradation study 
was better than that achieved on site, and the reasons for that is either the quality of the 
spiked water or the accuracy of the work in the field is less than that in the laboratory. 
Another recovery test for progestogens was achieved with the final effluent in two 
occasions and in two different locations. A big container of 20l of final effluent samples 
were taken from Cranfield University sewage treatment work at the same day, each 
sample was 1l; five samples were unspiked, five samples were spiked at 5ng, and 
another five samples were spiked at 10ng in order to find the recovery percentage of the 
method. In addition, eight samples were collected from GAC effluent (final effluent) at 
Hallam Fields STW, each sample was 1l and four of these samples were spiked at 5ng 
and compared with the collected unspiked GAC samples in order to validate the method, 
the results are listed in the Table 3.12.  
Table 3.11 Recovery data for progestogens from MilliQ water. 
Sample Name  CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Hal
lam 
Fields 
& 
Newt
hor
pe STW
s Recovery (1) 126 151 108 162 88 117 94 130 92 96 
Recovery (2) 116 129 286 167 173 107 125 211 141 182 
Recovery (3) 75 -34 68 0 4 56 58 8 -22 -34 
Recovery (4) 125 120 95 79 54 107 57 111 7 66 
Mean 111 91 139 102 80 97 83 115 54 77 
RSD % 22 93 71 77 89 29 39 72 138 115 
  De
gra
dat
ion
 
Stu
dy
 
Recovery (1) 104 105 71 102 107 102 77 107 71 84 
Recovery (2) 98 108 72 97 106 97 101 119 80 97 
Recovery (3) 101 102 83 98 100 99 104 109 92 84 
Recovery (4) 101 103 84 106 95 104 101 118 91 95 
Mean 101 104 78 101 102 100 96 114 83 90 
RSD % 2 3 9 4 5 3 13 5 12 8 
                                                                                                                                                             Chapter Three 
  
53 
 
Table 3.12 Recovery data for progestogens from final effluent and GAC effluent. 
   CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Cra
nf
ield
 Un
iversi
ty 
STW
 
Final effluent (n=5) 
spiked at 5 ng/l                      
% Mean recovery  95 129 84 100 72 125 78 110 78 72 
%RSD 9 45 12 7 37 10 15 36 11 16 
Final effluent (n=5) 
spiked at 10 ng /l                      
% Mean recovery  117 106 105 103 101 105 84 116 80 79 
%RSD 11 12 34 7 36 9 4 26 9 27 
Ha
lla
m 
Field
s STW
 GAC Effluent (n=4) 
spiked at 5 ng/ l            
% Mean recovery  95 96 110 70 95 100 78 72 49 57 
%RSD 17 21 30 30 56 21 18 34 41 58 
 
Benzotriazoles 
Table 3.13 represents the recovery data for benzotriazole of all sample batches that 
were undertaken during the study. Each sample was one litre of MilliQ water and spiked 
in different levels. Samples were taken from STWs (Hallam Fields and Newthorpe), 
Erewash River, tap water, and the degradation study in addition to some initial 
laboratory studies to validate methods. The recoveries of the samples were very good; 
the mean recovery was 95% and 101% for BT and TT respectively in the glass bottles. In 
plastic bottles, the recovery for TT was the same as in the glass bottles, but the recovery 
of BT was 91%. 
 
 
 
 
 
 
 
                                                                                                                                                             Chapter Three 
  
54 
 
Table 3.13 Recovery data for benzotriazoles. 
Sample Name Lab Recovery % BT  TT 
Hallam 
Fields & 
Newthorpe 
STWs 
Lab Recovery (1) 134 155 
Lab Recovery (2) 102 120 
Lab Recovery (3) 113 111 
Lab Recovery (4) 121 122 
Erewash 
River 
Lab Recovery (1) 109 107 
Lab Recovery (2) 93 95 
Lab Test 
Lab Recovery (1) 91 94 
Lab Recovery (2) 79 74 
Lab Recovery (3) 81 86 
Lab Recovery (4) 79 85 
Lab Recovery (5) 63 87 
Lab Recovery (6) 85 82 
Lab Recovery (7) 82 90 
Mean 95 101 
RSD % 21 22 
  
Plastic Bottles   
Tap water 
Lab Recovery (1) 118 98 
Lab Recovery (2) 99 103 
Lab Recovery (3) 73 115 
Lab Recovery (4) 74 88 
Mean 91 101 
RSD % 24 11 
 
 
3.2 Field studies. 
This research involved a number of surveys involving sampling of water and effluents. 
These can be divided into three types, from the survey of STW (November 2008), the 
samples from The River Erewash (January and October 2009) and the tap water survey 
during May and June 2010. This section describes these events. 
3.2.1 Sampling of wastewater at Hallam Fields and Newthorpe  
Two STWs were selected for study the removal of progestogens and benzotriazoles 
during unit processes. Each of the STW discharged into the River Erewash. One 
(Newthorpe STW) was a trickling filter (TF) plant, with a rapid sand filter, and dry 
weather flow (DWF) of 10,282 m³/day. Three sampling points were selected through 
                                                                                                                                                             Chapter Three 
  
55 
 
the processes which were: settled sewage, after trickling filter, and after the sand filter 
(final effluent) as shown in Figure 3.7. 
 The other site (Hallam Fields STW) was a nitrifying activated sludge (N/AS) works, also 
with a sand filter, treating a DWF of 10,022 m³/day. Sampling points were at seven 
locations through the process which were four points in the conventional treatment 
represented by: crude, settled sewage, then after the biological treatment and finally 
after the sand filter (final effluent). For the advanced wastewater techniques, three types 
of advanced treatment were available and the sampling points were in three parallel 
streams which were: after the ozone tank, after the GAC tank, and after treatment with 
chlorine dioxide. These three systems were working in parallel. Each system treated 
between 200 to 1,000 m3 of the effluent from the sand filter per day. Ozone was 
generated from liquid oxygen on site. The GAC treatment used coal-based activated 
carbon operated at a minimum 20 min empty bed contact time (EBCT). In order to 
produce ClO2, hydrochloric acid, sodium hypochlorite solution and sodium chlorite 
solution were mixed on site. The dose into final effluent of ozone and ClO2 was at a rate 
of 1mg/l.  Figure 3.7 shows the sampling points at Hallam Fields STW. 
Sampling was in November 2008 for four days from Monday to Thursday for both sites. 
The sampling was at two times for Hallam Fields STW, once at 9:00 am and the other 
batch of sampling was at about 2:00 pm. At Newthorpe STW, the sampling was once a 
day at 12:00 pm. Samples were collected in 2.5l amber glass bottles and filtered by 
(GF/C, whatman, UK) directly after collection and were then extracted onto SPE. 
Because of the concentrations of benzotriazoles collected from the first sampling 
campaign (November 2008) were out of the calibration curve for the samples from 
advanced treatment, one further day of sampling was undertaken on 16th of September 
2009 from the Hallam Fields STW. Samples were collected by the staff at STW and sent 
to Brunel University, each sample was 100ml with 0.1ml of the internal standards. They 
were collected from the final effluent, post ozone, post GAC, and post ClO2 at two times 
(one in the 9:00 am and the other was in 2:00 pm) to be within the calibration curve.   
A crude and settled sewage sample of 500ml and 200ml for progestogens and 
benzotriazoles samples respectively. All sample for biological process, sand feed, final 
effluent and advanced treatment samples were 1000ml for progestogens. For 
Benzotriazole, all samples were 200ml except the advanced treatment samples were 
100ml. Table 3.14 summarises the sampling volume of each sampling point in the STW. 
                                                                                                                                                                                                                                                                   Chapter Three 
            
56 
 
 
Figure 3.7 Flow diagram and sampling points for Hallam Fields (top) and Newthorpe STWs. 
 
                                                                                                                                                             Chapter Three 
 
57 
 
Table 3.14 Sampling volume of each sampling point in the STW. 
Sampling Point Sample Volume (l) 
  Progestogens Benzotriazoles 
Crude sewage  0.5 0.2 
Settled sewage 0.5 0.2 
RGF feed 1 0.2 
Final effluent 1 0.2 
Ozone output 1 0.1 
GAC output 1 0.1 
ClO2 output 1 0.1 
 
 
 
3.2.2 Sampling of the Erewash River 
The River Erewash is a tributary of the River Trent and it rises in Kirkby-in-
Ashfield, Nottinghamshire. The River Erewash drains an area of 211 km2 above its 
confluence with the River Trent near Nottingham, UK. The mean flow of the River 
Erewash is 1.91 m3/sec.  Around 30% of the catchment is covered in urban development 
with the rest mainly arable and grazing (Marsh, Greenfield & Hannaford, 2005). There 
are eight sewage treatment works which discharge along the River Erewash.  
Two sampling campaigns were conducted in order to determine the concentration of 
benzotriazoles and progestogens in the river and the STW existing in the Erewash River, 
the first campaign was in January 2009 and the second one was in October of the same 
year. There were 24 sampling points including eight wastewater treatment effluents 
existing on the river. The grid references of 11 sampling point along the River Erewash 
are in Table 3.15. The other five sampling points were on the brooks, tributaries, to the 
River Erewash. Samples were collected in 2.5l amber glass bottles with 
CuSO4.5H2O/nitric acid preservative. Sample volume was 1l for progestogens and 200 
ml for benzotriazoles and they were filtered and extracted after less than 24 hours of 
collection. Figure 3.8 shows the sampling point on the River Erewash, on its brooks, and 
emission points of benzotriazoles from eight STWs.  
                                                                                                                                                                                                                                                                   Chapter Three 
 
58 
 
Table 3.15 Grid references of the sampling point along the River Erewash. 
Sample No. Location on river system Grid references 
1 Erewash U/S of Kirkby STW SK 485548 
2 Kirkby STW FE  
3 Erewash D/S Kirkby STW (and U/S of Pinxton STW) SK 464547 
4 Pinxton STW FE  
5 Erewash D/S Pinxton STW (and U/S of Pye Bridge STW) SK 443529 
6 Pye Bridge STW FE  
7 Erewash D/S Pye Bridge STW SK 440520 
8 Bagthorpe brook  
9 Nethergreen brook  
10 Erewash U/S of Milnhay STW SK 455466 
11 Milnhay STW FE  
12 Erewash D/S of Milnhay STW SK 463454 
13 Gilt brook U/S of Newthorpe STW  
14 Newthorpe STW FE  
15 Gilt brook D/S of Newthorpe STW  
16 Erewash D/S of Gilt brook confluence SK 475444 
17 Erewash U/S of Hallam Fields STW SK 478405 
18 Hallam Fields STW FE  
19 Nut brook  
20 Erewash D/S of HF STW & Nut brook confluence (and U/S of Stapleford STW) SK 484383 
21 Stapleford STW FE  
22 Erewash D/S Stapleford STW (and U/S Toton STW) SK 503341 
23 Toton STW FE  
24 Erewash D/S of Toton STW ( and just before confluence with R. Trent) SK 510335 
                                                                                                                                                             Chapter Three 
 
59 
 
 
Figure 3.8 Schematic diagram of the sampling points on the River Erewash and 
its brooks. Numbers refer to locations identified in Table 3.15. 
 
3.2.3 Sampling of tap water  
To determine whether there were any benzotriazoles  in the potable supply, we 
undertook sampling on four occasions for 20 tap water points during May and June 
2010 for a total of eighty tap water samples, from locations in the south east of England, 
these sampling points were predominantly within a 15 mile radius of Uxbridge, in west 
London, although some were up to 30 miles to the west and one location was 80 miles to 
the north east. One litre of the each sample was collected in the morning and they were 
then extracted within less than five hours of collection. 
 
3.2.4 Domestic dishwasher powders and tablets 
During May and June 2010, consumer products were purchased from UK supermarkets 
and then analysed in order to quantify the benzotriazoles concentration in the 
dishwasher powder and tablet, approximately 20 g of each product collected from six 
brands of dishwasher powder and tablet were weighed and dissolved in 1l of MilliQ 
Glit Brook 
Nethergreen 
Brook 
Bagthorpe 
Brook 
Nut Brook 
                                                                                                                                                             Chapter Three 
 
60 
 
water by using a magnetic stirrer. Duplicated samples were analysed after one hour of 
dissolution. Then, further dilutions (1:100) and some samples had more dilution in 
order to be with the range of calibration standards.  An external standard was used to 
analyse the samples to quantify the benzotriazoles. Table 3.3 shows the retention time 
and the masses used to quantify benzotriazoles. 
 
3.3 Degradation study 
The goal of studying the degradation of progestogens and benzotriazoles in rivers was to 
determine the half life of these chemicals. Therefore, two plastic tanks each one about 
100l in volume was filled with about 60 l of water taken from the Grand Union Canal 
side River in Maple Cross, Hertfordshire, about 0.5 km downstream of maple Lodge STW 
(Figure 3.9). Each tank had one air pump and this pump distributed the air via two 
bubble diffusers in the tank in order to maintain the dissolved oxygen levels. In addition 
to that, two agitators with two magnetic bars were installed in each tank in order to 
keep the water mixed. For two weeks, dissolved oxygen, pH and temperature were 
measured every day in the morning from each tank. Also, samples were taken from each 
tank in the morning for progestogens and benzotriazoles. The sample volume of 
progestogens was 1l, and for the benzotriazoles was 200ml. Duplicate samples for 
progestogens and benzotriazoles was collected in days 1, 4, 9, and 14 of the study. Four 
samples representing laboratory Recoveries were analysed during the study and the 
percentage of recovery of all chemicals were from 78% to 114% (Table 3.11). Four 
samples for progestogens and two samples for benzotriazoles each one was 1l of MilliQ 
water was used as blank sample, the mean concentration of all chemicals were between 
0.4 and 3.4 ng/l (Table 3.9) (Table 3.10).  
The half lives of these 12 compounds (progestogens and benzotriazoles) were calculated 
according to the equation (1): 
Half life (t1/2) = ln2/k tot.  ………….. (1)       
Where ktot. represents the overall degradation rate of the compound (Sinkkonen & 
Paasivirta, 2000). 
                                                                                                                                                             Chapter Three 
 
61 
 
 
Figure 3.9 Location of the sampling point for the degradation test, about ≈ 850m 
downstream Maple Lodge STW (Google Earth). 
 
3.4 Modelling 
In collaboration with Richard Williams at the Centre of Ecology and Hydrology (CEH), 
this work involved visiting CEH in order to see the approach used for River Erewash 
modelling and its catchment area. The model was run by Richard Williams using the 
data provided from the first sampling campaign only of Hallam Fields and Newthorpe 
STWs for progestogens and benzotriazoles in the influent and final effluent. A single 
grab sample was collected from the River Colne (tributary of the River Thames) in order 
to investigate the occurrence of these compounds. Therefore, the Thames River 
catchment area was also modelled to evaluate their wider occurrence in the UK. The first 
approach was used by predicting the concentrations in the River Erewash by using the 
final effluent concentrations that measured at STWs and the second approach was 
depending on the per capita load. The catchments modelled were those of the River 
                                                                                                                                                             Chapter Three 
 
62 
 
Trent, where the Erewash is located, and the River Thames, which was the known 
source for some of the tap water samples, in particular from the area around Uxbridge, 
west London.  
3.4.1 Overview of the model 
Modelling was carried out using the LF2000-WQX model Williams et al. (2009), which is 
a system designed for making predictions of river concentrations of chemicals which are 
disposed of “down-the-drain” ( i.e. chemicals whose main entry to the river system is 
through sewage treatment works discharges).  It is based on the simple mass balance 
mixing equation which is applied in a Monte Carlo simulation using the method of 
combining distributions proposed by (Warn & Brew, 1980). Good estimates of river flow 
are important to correctly estimate in-stream concentrations resulting from point 
source discharges.  In LF2000-WQX, river flow is calculated using the well established 
LowFlows 2000 hydrological model which estimates the flow duration curve (i.e. the 
statistical distribution of flows) at ungauged stations (Keller & Young, 2004; Young, 
Grew & Holmes, 2003).  Point-source effluent emissions are combined with reach-
specific flow statistics to calculate in-river concentrations after mixing at the point of 
discharge taking account of concentrations coming from upstream.  Concentration 
changes along the river network due to dilution from tributaries not receiving 
discharges and degradation are taken into account. Accumulation in other 
environmental compartments (e.g. sediments) is not considered. The result is a 
statistical distribution of calculated in-river concentrations for each river reach, based 
on the variability of reach-specific river discharge, emissions from the STWs in the 
upstream catchment as well as in-stream degradation (Price et al., 2010). 
3.4.2 Method of extrapolation to the Trent basin 
To run the model at a catchment scale, to obtain values for sewage treatment works 
discharges that could be used more widely throughout the catchment, the measured 
concentrations in effluents were transformed into equivalent per capita output loads 
(equation 2).  
 
                          …………………..…… (2) 
Where PCLi (ng/person/day) is the per capita load for chemical i, Ceff (ng/l) is the 
measured effluent concentration, DWF (m3/s) is the dry weather flow from sewage 
                                                                                                                                                             Chapter Three 
 
63 
 
treatment works j and Pop is the population served by the works and A is a unit 
conversion factor. To do that, these steps were followed to calculate the load per capita. 
 
1. Calculate a per capita load in the effluent from the eight sewage treatment works on 
the Erewash based on the measured effluent concentrations of BT and TT. This is 
simply the measured concentration multiplied by the dry weather flow from the 
STW divided by the number of people served by the works. The values are given in 
Table 3.16. 
2. Find an average per capita value checking if there was any difference between types 
of STW. If all STWs are the same then we can calculate one average value and a 
standard deviation.  
Ofwat, water services regulation authority, in 2008 classified STWs into seven 
different categories in order to discriminate between different treatment processes 
in terms of their pollutant removal efficiency (Ofwat, 2008). Some of these 
classifications relavant to the works on the Erewash are: 
SAS (Secondary activated sludge): As primary, plus STWs whose treatment 
methods include activated sludge (including diffused air aeration, coarse bubble 
aeration, mechanical aeration, oxygen injection, submerged filters) and other 
equivalent techniques including deep shaft process, extended aeration (single, 
double and triple ditches) and biological aerated filters as secondary treatment. 
TA2 (Tertiary A2): STWs with a secondary activated sludge process whose 
treatment methods include rapid-gravity sand filters, moving bed filters, pressure 
filters, nutrient control using physico-chemical and biological methods, disinfection, 
hard chemical oxygen demand (COD) and colour removal, where used as a tertiary 
treatment stage. 
TB2 (Tertiary B2): STWs with a secondary biological process whose treatment 
methods include rapid gravity sand filters, moving bed filters, pressure filters, 
nutrient control using physico-chemical and biological methods, disinfection, hard 
COD and colour removal, where used as a tertiary treatment stage (Ofwat, 2008). 
3.  A Welsh 2-way t-test showed that SAS type STWs had a significantly lower per 
capita effluent values than either TA2 or TB2 and so two values were calculated 
(Table 3.17). Actually this is rather surprising as it would be expected that tertiary 
treatments would remove more organic chemicals in general.  
                                                                                                                                                             Chapter Three 
 
64 
 
4. So now we can set up all STW input per capita loads in the River Trent to be the 
effluent per capita loads calculated above from the non-SAS type works. For these 
works a removal efficiency of 0% was applied (i.e. the input per capita load was the 
same as the effluent per capita load as we measured effluents). For SAS works 
removal efficiencies of 37.3% and 50.1% were set for BT and TT removal 
(253/678*100 and 728/1452*100) respectively. 
 
 
 
                                                                                                                                                                                                                                               Chapter Three 
 
65 
 
Table 3.16 River Erewash sewage treatment works and calculated per capita effluent loads. 
 
  
STW 
  
Type 
DWF 
m3/s 
DWF 
m3/day 
Concentration 
(ng/l) Population Mass (g/d) PerCap (μg/day) 
BT TT  BTm TTm BTcap TTcap 
Kirkby SAS 0.069 5970 840 2685 24538 5.0 16.0 204.4 653.3 
Pinxton TA2 0.049 4242 1335 4125 8166 5.7 17.5 693.5 2142.9 
Pye Bridge TB2 0.024 2048 2895 5450 7043 5.9 11.2 841.7 1584.5 
Milnhay TA2 0.082 7050 1655 3400 25957 11.7 24.0 449.5 923.5 
Newthorpe TB2 0.119 10282 2470 5500 43382 25.4 56.5 585.4 1303.5 
Hallam Fields TA2 0.116 10022 2090 5700 44895 20.9 57.1 466.6 1272.5 
Stapleford SAS 0.066 5737 1375 3665 26203 7.9 21.0 301.0 802.4 
Toton TB2 0.194 16762 3605 5200 58584 60.4 87.2 1031.4 1487.8 
 
Table 3.17 Summary of per capita loads (µg/day) calculated from effluent data from STWs on the River Erewash. 
 TA2 & TB2 SAS 
 Mean STDEV Mean STDEV 
BT 678 227 253 68 
TT 1452 407 728 105 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Chapter Four:  Results of Conventional Treatment 
 
  
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                Chapter Four 
 
67 
 
Overview 
Primary treatment, biological treatment and sometimes tertiary treatment which is 
usually designed to remove ammonia or suspended solids are the main components of 
conventional wastewater treatment. This chapter will report the occurrence of the 
compounds of interest in these three stages at Hallam Fields and Newthorpe STWs. 
Therefore, samples were taken after each unit process in order to observe the 
occurrence of these chemicals and to evaluate how effective each unit process was at 
removing them. In addition, some operation parameters and physiochemical parameters 
will also be described. 
4.1  Physiochemical parameters and sampling conditions. 
The two STWs were sampled during November 2008. The biological treatment at 
Hallam Fields (Figure 4.1) was N/AS served 44,895 population equivalent (PE).  The 
second STW, Newthorpe, utilised trickling filters as a biological treatment and served 
43,382 PE (Figure 4.1). The main sanitary parameters of these sewage treatment works 
are listed in Table 4.1 and represent the mean of eight and four samples from Hallam 
Fields and Newthorpe STWs respectively.   
 
Figure 4.1 Photographs of the two sewage treatment works, Hallam Fields (left) 
and Newthorpe (right). 
                                                                                                                                                                                                                                                                      Chapter Four 
 
68 
 
 
Table 4.1     Operating parameters for sewage treatment works. 
Operating Parameters   Hallam Fields STW Newthorpe STW 
Biological process   Activated Sludge Process Trickling Filter 
PE  44,895 43,382 
Flow (DWF)   10,022 m³/day 10,282 m³/day 
Parameter Unit Settled Sewage ASP Effluent Final Effluent Removal % Settled Sewage Humus Tank Effluent Final Effluent Removal % 
pH   8.0 7.9 7.9   8.0 7.9 7.8  
Ammoniacal Nitrogen as N  mg/l 14.6 0.3 0.3 98 23.0 1.3 0.5 98 
Nitrogen, Total Oxidized as N  mg/l 1.7 14.9 14.7   0.4 24.8 21.6  
Phosphorus , Total as P mg/l 3.2 0.8 0.7 77 5.1 0.9 0.3 93 
BOD + ATU (5 day)  mg/l 52.9 2.0 1.0 98 80.3 3.3 1.0 99 
COD (Total) mg/l 144.0 23.6 24.1 83 240.8 43.5 29.3 88 
          
                                                                                                                                                                Chapter Four 
69 
 
According to the results shown in Table 4.1, the removal efficiency of BOD5 was 98% 
and 99% for Hallam Fields and Newthorpe STWs respectively. Ammoniacal nitrogen as 
N was also removed with 98% removal efficiency at both STWs. Although suspended 
growth as N/AS plant may give more removal, however TF STW has shown good 
removal efficiency for phosphorus compared to the N/AS STW represented by 93% and 
77% removal efficiency respectively, this perhaps because of few numbers of samples 
and time of sampling might have biased the results. It is apparent from this table that 
there was no variation in pH in settled sewage and final effluent for both STWs. Despite 
of high concentration of COD in Newthorpe STW compared to Hallam Fields STW, the 
removal efficiency of COD at trickling filter process was higher than nitrifying activated 
process, which was not expected according to previous literature and that might be 
again due to sampling bias. During the sampling, there was no rain or wet weather; as a 
result the concentrations of the chemicals of interest in the influent would be expected 
to be at relatively high concentrations due to the lack of dilution, giving high loadings to 
the STWs.  
 
Sampling bias 
The daily volumes of wastewater streams were very large. In addition, the analytical 
costs of pharmaceuticals in aqueous samples are more expensive than other compounds.  
Therefore, samples must be collected in order to represent the concentration of selected 
chemicals in wastewater. Table 4.2 shows the sampling regime achieved through the 
study the occurrences and removal of progestogens and benzotriazoles at the two STWs. 
At Hallam Fields STW, two sampling times per day were achieved, the first sampling 
time was at 9:00 am and presumably if the retention time in the sewer system was 6 or 
9 hours, in both cases that would mean that concentrations of these compounds were 
weak as inputs occurred at night. In the mean while, the second sampling time was at 
2:00 pm and in this case the concentrations would be stronger in the effluent than at the 
influent. Thus this lag time may have had an effect on calculating the removal efficiency, 
making it to be lower than the true value. 
Newthorpe STW had only one single sample per day and that was at 12:00pm, this 
means possibly strong concentrations in the influent and weak concentrations in the 
                                                                                                                                                                Chapter Four 
70 
 
effluent, consequently good removal efficiency will be determined. Generally, all these 
limitations, sampling time and sample numbers, might have led to some bias in the 
results and therefore there is associated uncertainty in the results.   
Table 4.2 Sampling regime achieved at the two conventional STWs. 
  time of discharge to 
sewer 
STW Sampling time time in sewer 6 hours  9 hours 
Hallam Fields 09:00 (weak) 03:00 (weak) 00:00 (weak) 
 14:00(strong) 8:00(strong) 5:00(strong) 
Newthorpe 12:00(strong) 06:00(weak) 03:00 (weak) 
 
4.2 Occurrence and removal of progestogens in 
conventional treatment works. 
The concentrations of progestogens after each process at Hallam Fields and Newthorpe 
STWs are shown in Figure 4.2. Concentrations of the chemicals of interest in the settled 
sewage, rapid gravity filter (RGF) feed, and final effluent are described below: 
 
4.2.1 Settled sewage 
The concentrations of progestogens after the primary settling tank at Hallam Fields and 
Newthorpe STWs are shown in Figure 4.2A. The natural hormone, progesterone (PGT), 
was detected and quantified in all the samples at this stage at both STWs. It can be seen 
that there was an abundance of progesterone, where the mean concentration was 46.9 
ng/l at Hallam Fields STW and was 41.6 ng/l at Newthorpe STW, no significant 
difference had occurred between both STW. Many compounds concentrations at both 
STW were similar, DHG and TBL mean concentrations in settled sewage at Hallam Fields 
STW was 35.4 and 29.4 ng/l, while at Newthorpe STW the mean concentrations of them 
were 35.2 and 15.9 ng/l. The cyproterone acetate (CPA) was quantified in seven out of 
eight samples with a mean concentration of 18.0 ng/l at Hallam Fields STW, and 
quantified in all samples with a mean of 13.5 ng/l at Newthorpe STW. MPA and DSP 
                                                                                                                                                                Chapter Four 
71 
 
were detected only in 25% of the samples of the settled sewage at Hallam Fields STW 
and 50% of the samples at  
 
 
 
Figure 4.2 Concentrations of progestogens in ng/l (A. Settled Sewage. B. RGF 
Feed.  C. Final Effluent) of two sewage treatment works. 
0 
10 
20 
30 
40 
50 
60 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Con
cent
ra
tio
n ng
/l 
Hallam Fields Newthorpe 
0 
10 
20 
30 
40 
50 
60 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Con
cent
ra
tio
n ng
/l 
0 
10 
20 
30 
40 
50 
60 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Con
cent
ra
tio
n ng
/l 
 
(A) 
Settled 
Sewage 
(B) 
RGF 
Feed 
(C) 
Final 
Effluent 
                                                                                                                                                                Chapter Four 
72 
 
Newthorpe STW, while NTD was quantified in half of the number of the samples and 
75% of the sample at Hallam Fields and Newthorpe STWs. MPA, DSP, and NTD show 
again no significant difference in concentrations for each individual compounds at each 
STWs, and the mean concentration of each individual compound was below 10 ng/l in 
both STWs.  
For a few compounds, significant differences (p=0.05) in concentrations were observed, 
Norgestrel in settled sewage at Hallam Fields STW 23 ng/l was a significantly above the 
concentration at Newthorpe STW of 6.1 ng/l. Conversely, MDP 6 ng/l and MTA 6 ng/l 
were significantly less at Hallam Fields STW than at Newthorpe STW of 23.9 ng/l and 17 
ng/l respectively.  
4.2.2 Rapid gravity filter (RGF) feed. 
The concentrations of progestogens after the biological treatment (N/AS or TF) at 
Hallam Fields and Newthorpe STWs are shown in the Figure 4.2B. It can be seen that 
significant difference (p=0.05) for progesterone had occurred between the settled 
sewage and the RGF feed indicating a removal of 92% and 90% for Hallam Fields and 
Newthorpe STWs respectively. According to Figure 4.2B, it was apparent that CPA, NTD, 
NGL and TBL show significant removal had occurred during the N/AS process at Hallam 
Fields STW, while these chemicals apart from CPA show no removal had occurred 
during the TF process at Newthorpe STW. This indicates that the activated sludge 
process (ASP) may be more efficient to remove these compounds than the TF process. 
Conversely, medroxyprogesterone (MDP) and MTA present a significant difference had 
occurred during TF as a biological process at Newthorpe STW, but there was no 
evidence for removal during N/AS and perhaps this because of these compounds had 
low concentrations entering the ASP at Hallam Fields STW.  The original data for 
progestogens in the conventional treatment processes are found in appendix 1. 
 For a few compounds, drospirenone (DSP), DHG, and MPA show no significant removal 
was observed during the biological treatment at both STWs. It is possible that more 
removal could occurred , but not statistically observed in this study and that probably 
due to the number of samples limits statistical power.  Generally, removal of compounds 
can be achieved by either adsorption or degradation and the range of Log Kow (3.87 ± 
                                                                                                                                                                Chapter Four 
73 
 
0.68) was similar for all progestogens. This means similar removals were expected in 
terms of adsorption and the differences in the removal might be resulted from the 
degradation. 
4.2.3 Final effluent 
Figure 4.2C shows the concentrations of progestogens after the RGFs at Hallam Fields 
STW and Newthorpe STW. From Figure 4.2C, it can be seen that all compounds 
demonstrated removal through the STW. Although it appears that the performance of 
the RGF at Newthorpe STW was better than the performance of that at Hallam Fields 
STW, however there was no significant difference (p=0.05) had occurred across the 
RGF’s for either STWs. Whereas the RGF at Newthorpe STW removal efficiency was 
between 53%-94%, and it was lower at Hallam Fields STW (0-62%). This difference in 
removal efficiencies may be real or might be biased because of the sampling strategy. 
The effluent mean concentration of each individual compound at Hallam Fields STW was 
below 7 ng/l, while the concentrations of the final effluents at Newthorpe STW were 
below 3.5 ng/l. Most of the final effluent samples concentrations were below their limit 
of quantification in both STWs, half of LOD value was taken to calculate the mean 
concentration of each compound. For example, there were only two values at Hallam 
Fields STW were above the quantification limit and these values had possibly influenced 
the results for  DSP, MDP, MTA, NTD, PGT, and TBL, therefore it is possible that  the 
performance of the RGF at Hallam Fields STW looked less efficient than the RGF at 
Newthorpe STW.  
The overall removal efficiency of progestogens during all the processes at each STW is 
illustrated in Figure 4.3. It is apparent that the natural hormone, progesterone, was the 
easiest compound which could be removed with 96% and 97% removal efficiency at 
Hallam Fields and Newthorpe STWs respectively. At Hallam Fields STW, the removal 
efficiency for most of the compounds were above 70% and only DSP and MPA were 
removed at 48% and 5% removal efficiencies, this is perhaps due to the low initial 
concentrations of these chemicals which were just above the limit of quantification. 
Newthorpe STW presented a very good removal for all compounds and the removal 
efficiencies were between 71% and 97%. In general, the ASP would be expected to give 
more removal than the TF process, however Hallam Fields STW looked less efficient to 
                                                                                                                                                                Chapter Four 
74 
 
remove these compounds than Newthorpe STW and as mentioned this may be due to 
sampling strategy. Therefore, it is possible that the removal efficiencies at Hallam Fields 
STW were more realistic than at Newthorpe STW. 
 
Figure 4.3  Percentage removal efficiencies of progestogens through the 
conventional treatment works. (1) Hallam Fields STW, (2) Newthorpe 
STW.  % removed during STW,  % Discharged to the surface 
water. 
4.3 Occurrence and removal of benzotriazoles in 
conventional treatment works. 
The results obtained from analyzing benzotriazoles at three different stages: settled 
sewage, biological treatment, and final effluent samples are illustrated in Figure 4.4. It is 
apparent that compared to progestogens there was an abundance of benzotriazoles that 
entered the STWs. Concentration of benzotriazoles were 2,000 to 3,500 ng/l compared 
to the tens of ng/l for progestogens. The proportions of BT to TT were the same at each 
STW. The results also showed that the concentrations of BT and TT in the settled sewage 
at each of the STW were the same, and although average concentrations of TT appeared 
to be above those of BT, there was no significant difference (p= 0.05). 
0% 
20% 
40% 
60% 
80% 
100% 
CPA 
1 
CPA 
2 
DSP
 1 
DSP
 2 
DHG
 1 
DHG
 2 
MDP 
1 
MDP 
2 
MPA 1
 
MPA 2
 
MTA 1
 
MTA 2
 
NTD 
1 
NTD 
2 
NG
L 1
 
NGL
 2 
PGT 
1 
PGT 
2 
TBL
 1 
TBL
 2 
Rem
oval
 %
 
                                                                                                                                                                Chapter Four 
75 
 
According to Figure 4.4, there was some evidence that removal had occurred during the 
biological treatment for BT in both STWs, since the concentration of RGF feed was 1,778 
and 1,438ng/l at Hallam Fields and Newthorpe STWs, but this difference was not 
significant and that possibly because of bias resulting from sample time/number.  There 
was also a significant difference in the removal for TT at Hallam Fields STW during the 
N/AS process, this means that TT has probably degraded because of low Kow log (1.24) 
meaning sorption is less likely. Although the data indicate removal occurred at 
Newthorpe STW, but that was not statistically significant. The original data for 
benzotriazoles in the conventional treatment processes are found in appendix 1. 
 
Figure 4.4 Concentrations of benzotriazole and tolyltriazole in (ng/l)  Hallam 
Fields STW, Newthorpe STW. 
Concentrations of these chemicals as they were discharged to the River Erewash in the 
final effluent were 1,523 and 1,567 ng/l for BT and TT at Hallam Fields STW and that 
would suggest a removal efficiency of 14% and 26% was achieved across the RGF, while 
the concentrations for BT and TT at Newthorpe STW were 560 and 830 respectively 
(Figure 4.4). No significant difference had occurred in the concentrations of 
benzotriazoles across the rapid gravity filters in both STWs. For BT or TT, a significant 
difference had occurred in the final effluent concentrations that discharged to the River 
Erewash between Hallam Fields STW and Newthorpe STW. 
0 
500 
1000 
1500 
2000 
2500 
3000 
3500 
4000 
Settled 
Sewage 
RGF Feed Final Effluent Settled 
Sewage 
RGF Feed Final Effluent 
Con
cent
rat
ion
  n
g/
l 
BT                                                                                          TT   
Flow 
                                                                                                                                                                Chapter Four 
76 
 
Although there is some evidence that removal had occurred through the conventional 
treatment works, but still there was a large amount of these chemicals were discharged 
to the surface water. Figure 4.5 shows the fluxes of benzotriazoles discharged from the 
conventional treatment works to the River Erewash which resulted from multiplying the 
flow by the concentration of these chemicals that discharge to the water body.  
 
Figure 4.5 Fluxes of benzotriazoles through the conventional treatment works 
in g/d.   Settled sewage,  Final effluent. 
From Figure 4.5, it is apparent that there was a removal had occurred through all 
process with an overall removal efficiency of 39% and 76% for BT at Hallam Fields STW 
and at Newthorpe STW respectively. Moreover, there was a significant reduction in the 
concentration of TT had occurred during the process of the STW at STWs, 52% for 
Hallam Fields STW and 72% for Newthorpe STW. In general, the removal efficiency at 
Newthorpe STW appeared higher than Hallam Fields performance and that might be 
real or because of the bias in the sampling number and time. 
Summary 
This chapter illustrated the occurrences of progestogens and benzotriazoles during the 
conventional processes: primary sedimentation, biological treatment, and rapid sand 
filter at sewage treatment works. Because of these emerging contaminants were not 
removed completely, therefore further study to observe their occurrence in the 
advanced treatment will be undertaken in the next chapter.  
0 
5 
10 
15 
20 
25 
30 
35 
Hallam Fields Newthorpe Hallam Fields Newthorpe 
                       BT                          BT                                    TT                          TT
g /
 da
y 
 
 
 
 
 
 
 
 
 
 
 
Chapter Five: Results of Advanced Treatments 
 
 
 
  
 
 
 
 
 
                                                                                                                                                             Chapter Five 
 
78 
 
Overview 
This chapter will report the effectiveness of the advanced treatment that was available 
at Hallam Fields STW. The effluents from three types of advanced treatment were 
sampled and analysed to determine the removal efficiencies of these techniques for the 
chemicals in this study. In total, eight samples were taken, one in the morning (9:00) and 
afternoon (14:00) for four days to monitor the removal of these chemicals via advanced 
technologies.  
5.1 Operation parameters for ozone, granular activated 
carbon, and chlorine dioxide. 
Part of the sand filter effluent was diverted to three pilot plants at Hallam Fields STW 
(O3, GAC, and ClO2) as shown in Figure 5.1. These three systems were working in 
parallel. Each system treated between 200 to 1000 m3 of the effluent from the sand filter 
per day. A dose of 1mg/l of ozone was injected by injection system into the effluent with 
three minutes contact time; ozone was generated from liquid oxygen on site. The GAC 
treatment used coal-based activated carbon operated at a minimum 20 min empty bed 
contact time (EBCT). In order to produce ClO2, hydrochloric acid, sodium hypochlorite 
solution and sodium chlorite solution were mixed on site; chlorine dioxide was injected 
into the effluent at a dose of 1 mg/l.  
 
    O3 system                      GAC system                ClO2 system 
Figure 5.1 Pictures of the advanced technologies at Hallam Fields STW. 
                                                                                                                                                             Chapter Five 
 
79 
 
5.2 Occurrence and removal of progestogens in the 
advanced treatment processes. 
In the following sections, performance of three processes in removing progestogens 
from the final effluent is presented.  For final effluent, although 75% of values were 
below limit of quantification for six compounds (DSP, MDP, MTA, NTD, PGT, and TBL) 
and only 2 values were above LOQ; however the mean concentrations of progestogens 
ranged between 0.5 ng/l for norethindrone to 6.7 ng/l for tibolone. All the original data 
for progestogens are in appendix 2.  
 
5.2.1 Removal by ozone 
The Figure 5.2 shows the concentrations of the progestogens pre - and post ozone 
treatment. It is apparent that the concentrations post ozonation were similar to those 
pre ozonation, with the mean concentrations of the post ozonation for these compounds 
ranging from 0.7 ng/l for norethindrone to 5 ng/l for norgestrel. There was no 
significant difference in any concentration as a result of treatment with ozone, thus, 
ozone apparently did not remove the progestogens. Because the concentrations of 
progestogens were close to or below the limit of quantification, and there were 
relatively few samples, therefore, there is a high degree of uncertainty associated with 
these data, as shown by the error bars in Figure 5.2.  
Five values out of eight sample concentrations for dydrogesterone (DHG), NTD, NGL, and 
TBL were less than the limit of quantification. These values were observed in the first 
two days of sampling (morning and afternoon). Half of the values of DSP, MDP, MTA, and 
PGT were below their quantification limit and that was in day 1 and 2 of sampling. The 
remaining compounds (CPA and MPA) had only two values under the limit of 
quantification and they were also observed in the afternoon of the first two days. 
Therefore, it is possible that there was analytical problem which occurred during the 
third and fourth days of the sampling (day three and four recoveries in Table 3.11) and 
that may have affected the average concentration of these compounds.  
                                                                                                                                                             Chapter Five 
 
80 
 
 
Figure 5.2 Removal of progestogens by ozone ( Final Effluent (Pre-O3),  Post-
O3). 
 
5.2.2 Removal by granular activated carbon (GAC). 
The occurrence and removal of progestogens through the GAC treatment are shown 
in Figure 5.3. The average concentrations of progestogens ranged from 0.2 ng/l for 
cyproterone acetate to 5.7 ng/l for tibolone. There was more evidence for removal 
than was observed during ozonation, however it was not statistically significant with 
p=0.05.  The average concentration of these compounds was calculated by assuming 
that each single value below the limit of quantification is equal to half of the limit of 
detection. Although no significant removal occurred, many compounds in the post 
GAC stage had 75% of values below LOQ and analytical uncertainty makes 
determining removal difficult. It was possible for some compounds like cyproterone 
acetate to show a significant difference between the final effluent (pre- GAC) and 
post GAC and that only achieved when p=0.1 and calculating the average based on 
1/10 LOD for these concentrations below their limit of quantification. 
0 
2 
4 
6 
8 
10 
12 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Co
nce
nt
ra
tion 
  n
g/
l 
                                                                                                                                                             Chapter Five 
 
81 
 
 
Figure 5.3 Removal of progestogens by GAC ( Final Effluent (Pre-GAC),  Post-
GAC). 
 
5.2.3 Removal by chlorine dioxide. 
The Figure 5.4 shows the occurrence and removal of progestogens through the chlorine 
dioxide treatment. The ranges of the mean concentrations were from 0.6 ng/l for 
norethindrone to 2.3 ng/l for drospirenone for the post ClO2 treatment. The mean for 
each compound was calculated based on ½ LOD for these values below LOQ. Although 
some removal had occurred in tibolone and dydrogesterone, however, there was no 
significant difference p=0.05 had occurred for these pharmaceuticals between pre and 
post ClO2 in the chlorine dioxide system. Again analytical uncertainty or few numbers of 
samples led to make determination of the removal efficiency for this technology difficult. 
For example each compound like drospirenone or progesterone had five values below 
the limit of quantification and only three values were above that, thus removal is 
calculated using very few measured values.  
0 
2 
4 
6 
8 
10 
12 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Co
nce
nt
ra
tion 
  n
g/
l 
                                                                                                                                                             Chapter Five 
 
82 
 
 
Figure 5.4 Removal of progestogens by chlorine dioxide ( Final Effluent (Pre-
ClO2),   Post- ClO2). 
 
5.3 Occurrence and removal of benzotriazoles in the 
advanced treatment process. 
For benzotriazoles, during November 2008, one litre of each sample and 1ml of internal 
standards was added to the sample. After analysing and the running the samples, the 
concentration of each sample was out of the instrument (LC (ESI+)/MS/MS) range of the 
calibration standards. The decision was made to sample 100ml (one in the morning and 
one in the afternoon) for one day from the Hallam Fields STW with 0.1ml of the internal 
standards to be within the calibration curve. Samples were collected by STW staff and 
sent to Brunel University on 16th of September 2009.  All the original data for 
benzotriazoles are in appendix 2.  
 
 
 
0 
2 
4 
6 
8 
10 
12 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Co
nce
nt
ra
tion 
  n
g/
l 
                                                                                                                                                             Chapter Five 
 
83 
 
5.3.1 Removal by ozone. 
The Figure 5.5 shows the concentrations of the benzotriazoles pre - and post ozone as an 
advanced treatment. Because a limited number of samples, it was difficult to examine if 
there was any significant difference had occur, however it was clear that there was a 
removal with a 74%, and the mean concentration of BT dropped from 517 ng/l to 136 
ng/l. Correspondingly, there was some evidence for removal of TT during the ozone 
treatment, but again that was not significantly proved due to the limited number of 
sample, however the concentration of TT had reduced from 2,253 ng/l to 467 ng/l 
achieving 79% removal efficiency.  
 
Figure 5.5 Removal of benzotriazoles by ozone ( Final Effluent (Pre-O3),  
Post-O3) 
5.3.2 Removal by granular activated carbon (GAC). 
The Figure 5.6 shows the occurrence and removal of benzotriazoles for the pre- and post 
GAC treatment. It can be seen that a clear reduction was achieved by GAC, since the 
concentration of BT decreased from 517 ng/l to 50 ng/l presenting a removal efficiency 
of 90%.  Interestingly, an excellent removal had occurred for TT with 98% removal 
efficiency and the concentration decreased from 2,253 ng/l to 51 ng/l.  The removal of 
TT looked higher than BT and this is probably due to the properties of each compound, 
since TT is more hydrophobic than BT and therefore a high removal was achieved 
during GAC system. 
0 
500 
1000 
1500 
2000 
2500 
3000 
BT TT 
Co
nce
nt
ra
tion
   n
g/
l 
                                                                                                                                                             Chapter Five 
 
84 
 
 
Figure 5.6 Removal of benzotriazoles by GAC ( Final Effluent (Pre-GAC),  
Post-GAC). 
5.3.3 Removal by chlorine dioxide. 
The occurrence and removal of benzotriazoles through the chlorine dioxide treatment 
are shown in Figure 5.7. It is apparent that there was a decrease in the BT concentration 
from 517 ng/l to  40 ng/l achieving 73% removal efficiency, however it was difficult to 
determine whether there was a significant difference or not due to the limited number 
of samples. In contrast, there was some evidence for a significant difference had 
occurred through ClO2 system for tolyltriazole. Therefore, it can be seen that a clear 
reduction to the pre chlorination concentrations from 2,253 ng/l to 469 ng/l as a post 
chlorination concentration. 
Table 5.1 summarises the removal efficiencies for the three technologies used as an 
advanced treatment to remove BT and TT from the final effluent. It is apparent that GAC 
was the most efficient technology among these technologies to remove these 
compounds.  
0 
500 
1000 
1500 
2000 
2500 
3000 
BT TT 
Co
nce
nt
ra
tion 
   n
g/
l 
                                                                                                                                                             Chapter Five 
 
85 
 
 
Figure 5.7 Removal of benzotriazoles by chlorine dioxide ( Final Effluent (Pre-
ClO2),  Post- ClO2). 
Table 5.1 Removal efficiencies for BT and TT through three different 
technologies. 
 Removal Efficiency % 
Advanced Treatment BT TT 
Ozone (O3) 74% 79% 
Granular activated carbon (GAC) 90% 98% 
Chlorine dioxide (ClO2) 73% 79% 
Summary 
This chapter illustrated the occurrences of progestogens and benzotriazoles during the 
advanced treatment process: ozone, granular activated carbon, and chlorine dioxide at 
Hallam Fields STW. In general, it is unlikely that progestogens would not be removed 
during the advanced treatment, while BT and TT would be removed. Although blanks of 
progestogens were subtracted from the values of each sample concentration, and 
because of high concentrations of progestogens in blank samples, it was possible that 
might lead to increase the uncertainty with the measured concentrations. Further study 
to observe the fate and behaviour of these compounds in the river water will be 
undertaken in the next chapter.  
0 
500 
1000 
1500 
2000 
2500 
3000 
BT TT 
Co
nce
nt
ra
tion 
  n
g/
l 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Chapter Six: The Fate of Progestogens and 
Benzotriazoles in the Laboratory 
Degradation Test 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                    Chapter Six 
 
87 
 
Overview 
This chapter will illustrate the behaviour of progestogens and benzotriazoles during the 
laboratory degradation study. Two tanks were filled with river water and preliminary 
analysis had shown that BT and TT concentration were enough to study degradation. 
The original concentrations of progestogens were very close to the quantification limit, 
therefore tanks were spiked only with progestogens analysis in order to make the 
concentration of progestogens quantifiable and consequently be able to study the fate of 
them during the two weeks. 
 
6.1 Basic parameters and initial concentrations. 
 
The parameters measured during the study were temperature, pH, and dissolved oxygen 
(DO).  The volume of river water in each tank was around 60l. All these parameters were 
measured once a day in each tank. Table 6.1 shows the volume of each tank and the 
mean of each parameter measured during two weeks. The initial temperature was 19 °C 
and the initial DO was 5 mg/l. Tanks were left for 24 hours to warm up and to stabilise 
the dissolved oxygen concentration and during that period temperature and DO were 
measured (after 8 hrs) and they were 21.2 °C and 7 mg/l respectively. The temperature 
was stable during the first ten days of the test and then there was gradually increasing in 
the temperature to reach 25 °C. The DO concentration varied from 7.0- 8.7 mg/l and this 
indicated that the tanks remained aerobic. 
The measured concentration of progestogens in ng/l at each tank on Day=0 are listed in 
Table 6.2. The samples of these concentrations were taken after one hour of spiking the 
tanks with progestogens in order to quantify these compounds. There was no need to 
spike the tanks with benzotriazoles; where the initial concentrations of BT in tank 1 and 
2 were 655 ng/l and 650 ng/l respectively, while the initial concentrations of TT were 
2,370 ng/l in tank 1 and 2,365 ng/l in tank 2. 
 
 
                                                                                                                                                                    Chapter Six 
 
88 
 
Table 6.1 Main measured parameters throughout the test (n=15). 
 
Parameter Units Tank 1 Tank 2 
Temperature (STDEV) °C 22.5  (±1.9) 21.8  (±2.0) 
pH (STDEV) - 8.5  (±0.51) 8.5  (±0.53) 
Dissolved Oxygen (STDEV) mg/l 8.0  (±0.36) 8.0  (±0.24) 
 
 
Table 6.2 Nominal concentrations for progestogens. 
 
 Compounds (ng/l) 
  CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Tank 1 538 663 532 646 548 568 507 532 401 662 
Tank 2 509 645 499 623 540 551 495 483 420 627 
 
` 
6.2 Degradation of progestogens 
 
The degradation of progestogens demonstrated differences between individual 
compounds. Some compounds were readily degraded and some were more recalcitrant. 
It is possible to split the ten compounds studied onto three groups according to their 
degradation rates, beginning with the natural hormone, progesterone, which was 
degraded rapidly, along with MDP and DHG. Figure 6.1 shows the concentration of 
progesterone over a period of 14 days and each point represent the average of 
concentrations in the two tanks.  It can be seen that the initial measured concentration 
was 410 ng/l in the tank and after 24 hours of aeration and mixing (at 20 °C), the 
concentration had reduced to 6 ng/l. Further decrease in the concentration of PGT had 
occurred in the next 24 hours, where the concentration had reduced to 4 ng/l. During 
the remaining period of the test, the concentrations of PGT were fluctuated between 
below the limit of quantification or just above it, probably because of either analytical 
uncertainty or other compounds like medroxyprogesterone (MDP) might be 
metabolised to produce PGT and that will increase the concentration of PGT to be above 
the LOQ and then reduced again to be less than LOQ.  
                                                                                                                                                                    Chapter Six 
 
89 
 
 
 
Figure 6.1 Concentration of progesterone throughout the 14 day test. 
 
Medroxyprogesterone and DHG also showed degradation during the study, where the 
concentrations had reduced from 515 ng/l and 635 ng/l for MDP and DHG to 5 and 2 
ng/l in 14 days achieving in that a degradation of 99.7% and 99.1% respectively. The 
concentration profiles of these compounds are shown in Appendix 3. 
The second group of compounds represented by NTD, NGL, TBL, and MTA showed a 
slower degradation during the study. It can be seen from Figure 6.2 that the mean 
concentration from the two tanks of norgestrel (NGL) dropped from 508 ng/l to 19 ng/l 
throughout the 14 day of the test. The other graphs of the other compounds are 
illustrated in Appendix 3. 
 
Figure 6.2 Concentration of norgestrel throughout the 14 day test. 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
PG
T n
g/
l 
Time (day) 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
NG
L   
ng/
l 
Time (day) 
                                                                                                                                                                    Chapter Six 
 
90 
 
Cyproterone acetate (CPA), MPA, and DSP as a third group showed least degradation 
during the study. For example, the initial concentration of CPA was 524 ng/l and after 14 
days, it was 85 ng/l. Figure 6.3 demonstrates the behaviour of CPA for two weeks 
throughout the test. Each point in the graph represents the mean of the concentration 
from the two tanks. The other compounds figures of this group are illustrated in 
Appendix 3. 
 
 
 
Figure 6.3 Concentration of cyproterone acetate throughout the 14 day test. 
 
 
As previously explained in chapter three, the half life of each compound was calculated 
according to the equation:  
Half Life (t1/2) = ln (2)/K tot.                                 ………………………….. (1) 
Table 6.3 shows the half lives of progestogens calculated according to equation (1) and 
also the degradation percentage of these compounds. Therefore, these compounds were 
divided into three groups according to their half lives. The first group which are PGT, 
MDP, and DHG, the half lives were less than 2 days.  It can be seen also that the 99% of 
PGT was degraded during the first 24 hours of the test, therefore it was not possible to 
calculate an accurate half life for the PGT and that because of a single data point was 
measured. Also the results showed that more than 90% was degraded in the 2nd and 7th 
day of the study for MDP and DHG respectively.   
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
CP
A   
ng/
l 
Time (day) 
                                                                                                                                                                    Chapter Six 
 
91 
 
The second group of compounds represented by NTD, TBL, NGL, and MTA, they 
demonstrate a half life between 2 to 4 days. It is apparent from Table 6.3 also that more 
than 90% of these compounds were degraded after 11 days for NTD and 12 days for the 
rest of this group. It also apparent from that the degradation rate according to the 
percentage degraded everyday was similar for most of these compounds in this group. 
The third group represents by DSP, MPA, and CPA demonstrated least degradation and 
therefore the half life for each compound was more than four days (Table 6.3). It is also 
can be seen from the table that more than 90% of DSP was degraded after 13 days of the 
test, while less than 90% was degraded for MPA and CPA throughout the test. 
 
 
 
 
 
                                                                                                                                                                                                                                                                         Chapter Six 
 
92 
 
Table 6.3 Degradation percentages and half lives for progestogens. 
 
  
Chemical Degradation % 
PGT MDP DHG NTD TBL NGL MTA DSP MPA CPA 
Da
y 
0 0 0 0 0 0 0 0 0 0 0 
1 99 74 45 15 5 6 16 15 13 13 
2 99 93 69 23 13 16 27 29 27 27 
3 >99 97 73 31 24 22 45 50 42 34 
4 99 98 78 37 35 32 48 57 46 44 
5 >99 99 82 51 43 39 55 64 49 45 
6 >99 99 88 60 60 52 62 69 56 51 
7 99 99 90 70 70 70 69 73 65 60 
8 >99 >99 93 75 71 71 73 82 71 65 
9 >99 >99 97 80 77 73 76 82 74 64 
10 >99 >99 99 84 80 77 79 82 78 65 
11 >99 >99 99 92 85 84 85 84 81 66 
12 >99 >99 99 94 92 90 90 87 88 76 
13 99 99 99 96 94 93 91 89 89 80 
14 99 >99 99 99 97 96 94 92 89 84 
Slope (K) -2.52 -0.673 -0.378 -0.273 -0.233 -0.217 -0.189 -0.17 -0.163 -0.12 
R Square 0.92 0.861 0.956 0.922 0.937 0.935 0.977 0.98 0.983 0.957 
Half life(day) <1 1.03 1.83 2.54 2.97 3.19 3.67 4.08 4.25 5.78 
                                                                                                                                                                          Chapter Six 
 
93 
 
6.3 Degradation of benzotriazoles 
For benzotriazoles, there was no need to spike the tank with BT and TT and that because of 
the preliminary analysis had shown that there was enough concentration of BT and TT to 
test their degradation. Therefore, each sample was 200 ml taken from each tank each day 
throughout the 14 day test and 1ml of internal standards was added to the sample. Figure 
6.4 shows the fate of BT through two weeks of study. Each point represents the measured 
concentration of each day from each tank. From Figure 6.4, the results show that the initial 
concentration of BT was 655 ng/l and 650 ng/l for tank 1 and 2 respectively. During the 
two weeks, the concentrations of BT were around these values with RSD of 4.1% and at the 
end of the test, there was a slightly increase in the BT concentrations and that probably due 
to the increasing in the temperature that could have caused evaporation, although these 
tanks were covered with a lid, might increased the concentrations. Original data are 
available in Appendix 3. 
 
 
Figure 6.4 Concentrations of BT and TT in each tank throughout the 14 day test 
(tank 1              and tank 2                ). 
 
0 
500 
1000 
1500 
2000 
2500 
3000 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
BT
  and
 TT
    ng
/l 
Time (day) 
BT 
TT 
                                                                                                                                                                          Chapter Six 
 
94 
 
In the mean while, the concentration of TT was 2,370 ng/l for tank 1 and 2,365 ng/l for tank 
2. For the period of the test, TT concentrations were around the initial concentration with 
RSD of 9.85% except the last four days of the test when a slight increase in the TT 
concentration had occurred, probably because of the temperature. Also it is apparent that 
both tanks had the similar pattern during the test (Figure 6.4). 
Figure 6.5 shows the mean concentrations of each compound that had been taken from 
each tank. It is apparent that the proportional between BT to TT was consistent. 
Benzotriazole and tolyltriazole showed no degradation had occurred throughout the test.  
 
Figure 6.5 Fate of benzotriazole and tolyltriazole throughout the 14 day test                                                          
(              BT and               TT). 
 
Summary 
This chapter illustrated the fate and behaviour of progestogens and benzotriazoles in the 
river water. The results show that progesterone was degraded rapidly, while the other 
compounds had a different degradation rates, and it was possible to categorise the 
progestogens into three groups according to their half life:  
0 
500 
1000 
1500 
2000 
2500 
3000 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
BT
 and
 TT 
  n
g/
l 
Time (day) 
                                                                                                                                                                          Chapter Six 
 
95 
 
 Group 1: half life of PGT, MDP and DHG < 2 days. 
 Group 2: half life of NTD, TBL, NGL and MTA between 2-4 days.  
 Group 3: half life of DSP, MPA and CPA > 4 days.  
For benzotriazoles, the results show no degradation had occurred throughout the test. 
These results for progestogens and benzotriazoles had led to investigate the occurrence of 
these compounds in the River Erewash, modelling the Trent catchment and Thames 
catchment to explore these compounds occurrences in wider area, and that what will be 
described in the next chapter. 
 
 
 
 
 
 
 
 
 
 
 
Chapter Seven: Results of Monitoring and Modelling of 
Progestogens and Benzotriazoles in River 
Erewash, Trent and Thames Catchments 
 
 
 
 
                                                                                                                                                                     Chapter Seven 
 
97 
 
Overview 
This chapter discusses the occurrence of progestogens and benzotriazoles in the River 
Erewash on the River Trent and its catchment, also the River Colne (tributary of the River 
Thames). Two sampling campaigns were achieved (each one represented by 24 sampling 
points including the effluent from eight STWs existing on the River) to observe the 
occurrences of progestogens and benzotriazoles in the River Erewash. A single grab sample 
was collected from the River Colne in order to investigate the wider occurrence of these 
compounds.  In addition, the modelling of River Erewash and the River Trent catchment 
area which is where the Erewash located are described in this chapter.  Thames River 
catchment area was also modelled to evaluate wider occurrence in the UK.  
7.1 Details of selected sewage treatment works. 
The types of the sewage treatment works and process details that were sampled during the 
survey are described in Table 7.1. During the sampling, the mean temperature river sample 
was 3.0 °C and 12.2 °C for January and October 2009 respectively. Average temperature of 
the final effluent samples was 7.8 °C in January and 15.3 °C in October.  
Table 7.1 Types of treatments existed in the eight STWs on the River Erewash.  
 
STWs Population DWF (m3/d) Type 
Kirkby STW  24,538 5,970 (SAS) N/ASP + ferrous chloride dosing  
Pinxton STW  8,166 4,242 (TA2) N/ASP + TFs + SFs + ferrous chloride dosing 
Pye Bridge STW 7,043 2,048 (TB2) TFs + SFs + ferric sulphate dosing 
Milnhay STW  25,957 7,050 (TA2) N/ASP + TFs + SFs + ferric sulphate dosing 
Newthorpe STW  43,382 10,282 (TB2) TFs + SFs + ferric sulphate/PAC dosing 
Hallam Fields STW 44,895 10,022 (TA2) N/ASP + SFs + ferrous chloride dosing 
Stapleford STW 26,203 5,737 (SAS) N/ASP + ferrous chloride dosing 
Toton STW 58,584 16,762 (TB2) N/ASP + TFs + SFs + ferric sulphate dosing 
           
 
                                                                                                                                                                     Chapter Seven 
 
98 
 
7.2 The occurrence of progestogens in the River Erewash. 
Two sampling campaigns were conducted in order to observe the occurrence of 
progestogens in River Erewash. After collecting the samples from the first campaign which 
comprised of 16 samples along the river and its tributaries, with eight samples of the final 
effluent of the STWs discharging to the river. Because of the gel permeation clean up 
problems that occurred, all samples from the first survey were lost due to the low pressure 
in the auto sampler and that led to collect the wrong fraction. Consequently, there was no 
signal could be seen when the samples were run by LC (ESI+)/MS/MS. The second sampling 
campaign was undertaken in October 2009. The same regime was followed as for sampling 
points and STW. There was high degree of uncertainty associated with the results and this 
uncertainty resulted from the values of the concentration of these compounds.  There was 
no rain at that time which led us to expect progestogens concentrations to be relatively high 
in the river. Table 7.2 shows the concentrations of progestogens discharged from eight 
STWs existing on River Erewash and the concentrations of progestogens were fluctuated 
around the limit of their quantification, however Pye Bridge STW was the highest in terms 
of discharging the progestogens among the STWs. Table 7.3 shows the concentrations of 
progestogens along the River Erewash in October 2009. It can be seen that only 
drosprinone and norgestrel were above their limit of quantification, while the rest of these 
chemicals were close to or just above their limit of quantification and some of them like the 
natural hormone (PGT) was below the limit of quantification along the Erewash River. 
Because they were unlikely to be detected and quantified, it was decided not to model these 
chemicals in the catchments or to monitor in the tap water. 
 
                                                                                                                                                                                                                                              Chapter Seven 
 
99 
 
Table 7.2 Concentrations of progestogens (ng/l) discharged from eight STWs existing on Erewash River. 
 
STWs 
Effluent from STWs ng/l 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
Kirkby (N/ASP)  < 0.2 2.2 2.3 1.3 0.6  < 0.4  < 1 7.2 0.5  < 1.6 
Pinxton (N/ASP)  < 0.2 5.7 2.5  < 0.4 1.1  < 0.4  < 1 2.9  < 0.4 12.1 
Pye Bridge (TF) 3.3 7.0 39.2 10.4 3.6 3.0 7.0 16.5 6.2 24.4 
Milnhay (N/ASP) 9.0 2.4 3.4  < 0.4 0.7  < 0.4  < 1 4.2  < 0.4 7.5 
Newthorpe (TF)  < 0.2 2.1 2.9 0.5 1.3  < 0.4  < 1 4.5  < 0.4 9.8 
Hallam Fields (N/ASP) 2.2 5.3 3.7 1.3 6.1 0.5 1.8 6.6  < 0.4 10.5 
Stapleford (N/ASP)  < 0.2 6.0 2.2 0.8 2.9  < 0.4  < 1 5.4  < 0.4 7.0 
Toton (N/ASP) 0.7 4.1 3.0  < 0.4 1.9  < 0.4  < 1 11.4  < 0.4 4.6 
 
 
Table 7.3 Concentrations of progestogens (ng/l) in Erewash River.  
 
Erewash River 
Concentration in Erewash River ng/l 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
U/S of Kirkby STW  < 0.2 4.0 3.6  < 0.4 0.8  < 0.4  < 1 4.3  < 0.4 2.5 
D/S Kirkby STW   < 0.2 4.4  < 1.6  < 0.4 1.3  < 0.4 1.1 4.3  < 0.4 4.6 
D/S Pinxton STW   < 0.2 1.8 3.9 0.6 1.1  < 0.4  < 1 4.2  < 0.4 3.1 
D/S Pye Bridge STW   < 0.2 2.0 2.0 0.6 1.1  < 0.4  < 1 3.2  < 0.4 2.1 
U/S of Milnhay STW  < 0.2 2.6 2.0 0.6  < 0.4  < 0.4  < 1 3.4  < 0.4  < 1.6 
D/S of Milnhay STW 3.1 4.5 2.0 0.5  < 0.4  < 0.4  < 1 4.7  < 0.4 4.1 
D/S of Gilt brook confluence 2.2 6.0 4.1  < 0.4 3.5 0.5  < 1 5.7  < 0.4 4.1 
U/S of Hallam Fields STW 2.8 2.5 2.1  < 0.4 0.6  < 0.4  < 1 1.7  < 0.4 3.8 
D/S of HF STW & Nut brook  1.8 2.5 4.9  < 0.4 1.4  < 0.4  < 1 3.7  < 0.4 4.0 
D/S Stapleford STW  1.8 9.6 2.3 0.5 2.3  < 0.4  < 1 5.7  < 0.4 1.7 
D/S of Toton STW  2.0 5.0  < 1.6  < 0.4  < 0.4  < 0.4  < 1 4.4  < 0.4 7.2 
 
                                                                                                                                                                     Chapter Seven 
100 
 
7.3 Occurrence of benzotriazoles in River Erewash 
7.3.1 The first survey in January 2009 
The flow rate of the River Erewash on 6th of January was 0.846 m3/sec and there had been 
no rain, indicating that the concentrations of benzotriazoles were also likely to be around 
their highest. The concentrations of benzotriazoles in the effluent samples from eight STWs 
existing on River Erewash are illustrated in Figure 7.1. It is apparent that the BT and TT 
were present in all the effluents of STWs. The treatment type, activated sludge or biological 
filters with or without tertiary treatment, had no clear relationship with the effluent 
concentrations. It can be seen that the concentration of BT was in the range from 840 ng/l 
at Kirkby STW to 3,605 ng/l at Toton STW with an average of 2,033 ng/l. In order to 
calculate the fluxes that were discharged from these STWs to the River Erewash, 
concentration of BT from each STW was multiplied by the discharge per day from each 
STW, and the results represent the total BT from each STW discharged to river. The 
summation of fluxes from eight STWs was 143 g/d. For tolyltriazole, the mean 
concentration of TT was 4,465 ng/l ranged from 2,685 ng/l at Kirkby STW to 5,700 ng/l at 
Hallam Fields STW, thus these STWs were discharging 291 g/d of TT everyday to the River 
Erewash.  The original data are found in appendix 4.    
  
                                                                                                                                                                     Chapter Seven 
101 
 
 
Figure 7.1 Final effluent concentrations of benzotriazoles from STWs,        BT,       TT, 
sites are shown as location downstream from the source of the river, left 
to right on x-axis in January 2009. 
The graphical representation of River Erewash showing the trend of benzotriazoles 
concentrations is illustrated in the Figure 7.2. It can be seen that there was an increase in 
the concentration of both BT and TT along the River and that concentrations of TT were 
also higher than BT, which was the same as in effluent from STWs. From the Figure 7.2, it 
can be seen that there was initial concentrations of BT and TT in the upstream of the river. 
In addition, these two compounds were present in all samples which were taken from 
brooks, small tributaries and the main river samples. Upstream the STW on the Gilt Brook 
was the highest among the tributaries on the Erewash River with 118 ng/l of BT and this 
means that there is a possibility that some industries or some effluent that discharged their 
effluent directly to the brook . It is obvious to notice that there was an increase in 
concentrations after about 2.5 km from the first sampling point and that resulted from the 
inputs from the first STW, and then the increase was continuous due to the inputs from the 
other STWs. At the same time, there was a decrease in the concentrations of these 
0 
1000 
2000 
3000 
4000 
5000 
6000 
Kirkby 
(N/ASP) 
Pinxton 
(N/ASP) 
Pye Bridge 
(TF) 
Milnhay 
(N/ASP) 
Newthorpe 
(TF) 
Hallam 
Fields 
(N/ASP) 
Stapleford 
(N/ASP) 
Toton 
(N/ASP) 
BT,
TT 
 ng/
l 
                                                                                                                                                                     Chapter Seven 
102 
 
chemicals in the river water at some points and that probably resulted from the confluence 
of less contaminated tributaries, leading to dilution. Each black arrow represents the input 
from the STW to the River Erewash, while the blue arrows represent the brooks that 
existed on the river itself. 
 
Figure 7.2 Graphical representation of the River Erewash showing concentrations 
in ng/l of BT           and TT            increasing downstream from the river 
source in January 2009.   
 
7.3.2 The second survey in October 2009. 
The second sampling survey was undertaken on the 29th of October 2009. There was also 
no rain on that day and the flow rate was 0.662 m3/sec. The concentrations of final effluent 
samples of the STWs existing on River Erewash are illustrated in Figure 7.3. It is apparent 
that once again, BT and TT were present in all sewage effluent samples. The mean 
concentration of the effluents from these STWs was 652 ng/l with a range from 496 ng/l to 
0 
500 
1000 
1500 
2000 
BT
  & 
TT
    ng
/l 
(21,38) 
(118,20) 
(23,35) (13,33) 
Nut Brook 
STW 1 
STW 2 
STW3 STW 4 
STW6 STW 7 STW8 STW 5 
Bagthorpe 
Brook Nethergreen Brook 
Gilt Brook 
                                                                                                                                                                     Chapter Seven 
103 
 
867 ng/l. While the average concentration of TT was 2,303 ng/l and varying between 2,040 
ng/l to 2,730 ng/l. According to the effluent concentration and flow rate from each single 
STW, the total amount of BT was discharged to the River Erewash was 40.8 g/d and 140 
g/d for TT. The original data are found in appendix 4. 
 
Figure 7.3 Final effluent concentration benzotriazoles from STWs,        BT,       TT, 
sites are shown as location downstream from the source of the river, left 
to right on x-axis in October 2009. 
According to the final effluent concentration from these STWs, the geographical 
representation of BT and TT along the River Erewash is illustrated in Figure 7.4. It can be 
seen that the concentration of BT at the upstream of the River was 51 ng/l. Because of the 
inputs from the STWs existed on the river, there was an increasing in the concentrations of 
BT in the river, but this increasing was only after the first and second STWs, then there was 
0 
1000 
2000 
3000 
4000 
5000 
6000 
Kirkby 
(N/ASP) 
Pinxton 
(N/ASP) 
Pye Bridge 
(TF) 
Milnhay 
(N/ASP) 
Newthorpe 
(TF) 
Hallam 
Fields 
(N/ASP) 
Stapleford 
(N/ASP) 
Toton 
(N/ASP) 
BT
 & 
TT
  n
g/
l 
                                                                                                                                                                     Chapter Seven 
104 
 
no wide variation in the concentrations although there was other STWs that discharge their 
effluent to the river and some tributaries with low concentration which might dilute the 
concentrations. 
For TT, it is apparent that the concentrations of TT were varied from 84 ng/l at the 
upstream of the river to 1,570 ng/l at some point and that was resulted from the fluxes of 
the STWs to the River Erewash. In addition, it is obvious to see the impact of these STWs on 
the trend of the River by increasing the concentration in the river and also the tributaries 
had an opposite effect to the impact of STWs by diluting the concentrations. 
 
Figure 7.4 Graphical representation of the River Erewash showing concentrations 
in ng/l of BT       and TT         increasing downstream from the river 
source in October 2009. 
In order to compare the occurrences of BT in the River Erewash in the two sampling 
campaigns (January and October), Figure 7.5 shows concentrations of BT along the River 
0 
500 
1000 
1500 
2000 
U/
S of
 Kirk
by 
ST
W
 
D/
S Kirk
by 
ST
W 
 
D/
S P
inxt
on
 
ST
W 
 
D/
S P
ye
 
Bri
dge
 ST
W 
 
U/S 
of 
Mil
nh
ay 
ST
W
 
D/
S of
 Mil
nh
ay 
ST
W
 
D/
S of
 Gi
lt 
broo
k 
con
flu
ence
 
U/
S of
 Ha
lla
m 
Fie
lds
 ST
W
 
D/
S of
 HF
 ST
W 
& Nu
t broo
k  
D/
S St
ap
lef
ord
 
ST
W 
 
D/
S of
 Toton 
ST
W 
 
BT
 & 
TT
    n
g/
l 
(16,29) 
(10,18) (31,35) 
(97,64) 
Nut Brook 
Gilt Brook 
STW 1 
STW 2 
STW 3 
Bagthorpe 
Brook 
Nethergreen 
Brook 
STW 5 
STW 4 
STW 6 STW 7 
STW 8 
                                                                                                                                                                     Chapter Seven 
105 
 
Erewash in the two occasions. It can be seen that the concentrations of BT were similar only 
in the first two points in the river and that reflect that the background concentration in the 
upstream was consistent. The concentration of BT was less in October than in January, this 
could be due to change in use, such as in dishwashing at catering for school lunches, as it 
was half-term in October 2009. Although the effluent concentration of BT at Kirkby STW in 
January was higher than in October, however, the trend of the concentration was similar 
between the first two points. Downstream Pinxton STW, it can be seen clearly the effect of 
Pinxton STW and then Pye Bridge STW on the BT concentration along the river in January. 
Because of the dilution that had  occurred due to the confluence between the River Erewash 
and some brooks, it can be seen the influence of these brooks on the BT concentration 
especially in January , while it is hard to find the effect of  these tributaries  in the BT 
concentrations on  October. 
 
Figure 7.5 Concentrations of BT along the River Erewash in the two occasions, 
January      (            ) and October (        ). 
0 
500 
1000 
1500 
2000 
U/S 
of 
Kirk
by 
ST
W
 
D/
S Kirk
by 
ST
W 
 
D/
S P
inxt
on
 
ST
W 
 
D/
S P
ye
 
Bri
dge
 ST
W 
 
U/
S of
 
Mil
nh
ay 
ST
W
 
D/
S of
 
Mil
nh
ay 
ST
W
 
D/
S of
 Gi
lt 
broo
k 
con
flu
ence
 
U/
S of
 Ha
lla
m 
Fie
lds
 ST
W
 
D/
S of
 HF
 
ST
W 
& 
Nu
t 
broo
k  
D/
S 
Sta
ple
ford
 
ST
W 
 
D/
S of
 Toton 
ST
W 
 
BT 
  ng
/l 
Jan. 
Oct. 
Nut Brook 
Gilt Brook 
STW 1 
STW 2 
STW 3 
Nethergreen 
Brook 
Bagthorpe 
Brook 
STW 4 
STW 5 
STW 6 STW 7 
STW 8 
                                                                                                                                                                     Chapter Seven 
106 
 
The concentrations of TT were also similar at the upstream of the river as shown in Figure 
7.6. The graph also shows that until downstream of Minhay STW, TT concentrations had the 
same pattern, and then due to the effect of the Gilt Brook and Newthorpe STW discharge to 
the River Erewash, since the TT concentration in October at Newthorpe STW was half the 
concentration in January. Therefore as a result of this impact the differences between 
January and October in TT concentration were consistent between that sampling point and 
just before the confluence with the River Trent.  
 
Figure 7.6 Concentrations of TT along the River Erewash in the two occasions, 
January       (         ) and October (       ). 
In general, although the flow rate in the River Erewash was in January higher than the flow 
rate in October, however the concentrations of BT and TT in the River Erewash looked 
higher in January than those in October. The reason for that is probably due the effluent 
0 
500 
1000 
1500 
2000 
U/
S of
 Kirk
by 
ST
W
 
D/
S Kirk
by 
ST
W 
 
D/
S P
inxt
on
 ST
W 
 
D/
S P
ye
 Bri
dge
 ST
W 
 
U/
S of
 Mil
nh
ay 
ST
W
 
D/
S of
 Mil
nh
ay 
ST
W
 
D/
S of
 Gi
lt broo
k 
con
flu
ence
 
U/
S of
 Ha
lla
m 
Fie
lds
 
ST
W
 
D/
S of
 HF
 ST
W 
& 
Nu
t broo
k  
D/
S St
ap
lef
ord
 ST
W 
 
D/
S of
 Toton 
ST
W 
 
TT 
   ng
/l 
Jan. 
Nut Brook 
Gilt Brook 
STW 1 
STW 2 
STW 3 
Nethergreen 
Brook 
Bagthorpe 
Brook 
STW 8 
STW 7 
STW 6 STW 5 
STW 4 
                                                                                                                                                                     Chapter Seven 
107 
 
concentrations of these chemicals which was discharged from the STWs to the river was 
higher in January than those of October occasion, and as long as these chemicals had shown 
no degradation had occurred in the river from the previous chapter, therefore, it would be 
expected that BT and TT concentrations in the River Erewash would be higher than October 
concentrations. 
7.4 Modelling of the River Erewash 
In order to validate the model, the model was examined in terms of the final effluent 
concentrations of these chemicals which were discharged from STWs, therefore when using 
the measured sewage works effluent concentrations to drive the inputs to the LF2000-WQX 
model, the fit for BT with the observed values slightly underestimated measured 
concentrations (regression slope = 0.8; R2 = 0.76; p<< 0.001) as shown in Figure 7.7. In 
contrast, it was able to reproduce the concentrations seen the river very well for TT, 
although there was a slight overestimate of the observed values (Figure 7.8). A regression 
of the observed against predicted TT values gave a line of slope = 1.2 and an R2 value of 0.88 
(p<< 0.001). This indicates that the municipal effluents were the predominant source of 
these compounds.       
         
Figure 7.7 Model outputs, showing observed (●) and predicted concentrations of 
BT along the river. Modelled values were calculated using measured 
effluent concentrations (solid line) and per capita loads (dotted line). 
 
 
 
5 0 0
 
 
 
 
1500
 
 5  10  15  20  25  30  35  
Di s t a n c e  d o wn  ri v e r (k m ) 
1 0 0 0
BT
 c
o
n
c
e
n
tra
ti
o
n
 (n
g
/L
)
                                                                                                                                                                     Chapter Seven 
108 
 
The model was also tested in terms of per capita load in order to validate it , thus the 
predicted concentrations calculated based on per capita loads give very similar fits to the 
observed data as those using the measured data (Figures 7.7 and 7.8). The average 
underestimate of the observed values was unchanged for BT and consequently the 
regression statistics was similar. For TT, the regression statistics were almost the same as 
using the measured effluent data with a slope of 1.3 and an R2 value of 0.87 (p <<0.001). It 
is clear that there were differences in the simulations although these were not large; the 
differences arise because per capita load is an estimation of the input from the sewage 
treatment works.  
 
 
Figure 7.8 Model outputs, showing observed (●) and predicted concentrations of 
TT along the river. Modelled values were calculated using measured 
effluent concentrations (solid line) and per capita loads (dotted line). 
 
For catchment modelling, it was not feasible to model the catchment in terms of using the 
concentrations of these chemicals from final effluent samples of the STWs, this is because 
these chemicals concentrations were not available from all STWs and for the whole 
catchment. In contrast, these results indicated that the calculated per capita loads in the 
10 00
20 00
30 00 
5 10 15 20 25 30 35 
D i s t a nce  d ow n r i ve r  ( km ) 
T
T
 
con
cen
tr
at
ion
 
(
n
g/
L)
                                                                                                                                                                     Chapter Seven 
109 
 
model for making predictions across the Trent catchment or Thames catchment would be a 
reasonable method for developing effluent concentrations at the unmeasured sites. 
 
 
7.5  Catchment modelling 
In order to save costs and resources of sampling and analysing many samples across the 
catchment, modelling was used to produce the concentration of benzotriazoles in the entire 
catchment by simulating the river Erewash to its catchment (Trent River catchment) based 
on per capita load. In addition and as long as there is no difference between the uses of 
these compounds in the area around River Trent catchment and the River Thames 
catchment, and also the operation types of the STWs was similar, therefore it was able to 
model the Thames catchment and the result was compatible with the real sample collected 
from one of the River Thames tributaries. 
 
7.5.1 Trent River catchment modelling. 
Across the River Trent catchment showed higher predicted mean concentrations of TT than 
of BT (Figure 7.9) because of its larger per capita input loads. Approximately 28% of river 
reaches showed BT predicted concentrations between 401 – 1,000 ng/l and 62% less than 
400 ng/l for the upstream areas and less impacted area by STWs inputs including the main 
river Trent for most of its length as shown in Figure 7.10.  For TT, 45% of concentrations 
were predicted to be between 401 – 1,000 ng/l with 90% less than 2,000 ng/l. The highest 
concentrations occurred just below sewage treatment works. The average concentrations of 
BT and TT across all the river reaches immediately downstream of a sewage treatment 
works discharge were 1,080 ng/L and 2,160 ng/l respectively (Figure7.9). 
                                                                                                                                                                     Chapter Seven 
110 
 
 
 
Figure 7.9 Model outputs for the River Trent catchment scale concentrations of 
benzotriazole and tolyltriazole (ng/l). 
 
 
 
7.5.2 Thames River catchment modelling. 
The purpose of modelling the Thames River catchment was to give an indication of the 
concentrations of BT and TT that might be found in the source water to water treatment 
works, in particular at Iver drinking water treatment which abstracts from the River 
Thames. Therefore a single grab sample taken from the River Colne, a tributary of the River 
Thames, in September 2010 to compare the average modelled values (BT 337 ng/l and TT 
508 ng/l) and measured values of 224 and 453 ng/l respectively and the results were 
compatible. Across the catchment, concentrations of BT were predicted to range from 1 to 
400 ng/l below the first STW inputs, with increasing values of 401 to 1,000 ng/l. While for 
TT, concentrations were predicted to range from 1 to 1,000 ng/l and frequently in the 1,000 
to 2,000 ng/l range in the lower reaches as shown in Figure 7.10.  
TT BT 
                                                                                                                                                                     Chapter Seven 
111 
 
 
Figure 7.10 Model outputs for the River Thames catchment scale concentrations of 
benzotriazole and tolyltriazole (ng/l).  
 
Summary 
This chapter illustrated the concentrations of benzotriazoles in the river waters. The 
modelling shows that these compounds were present in wide area of the catchments (Trent 
and Thames). Because of benzotriazoles were not degraded in the river water (according to 
the results in chapter 6), and the waters in these rivers are used as a sources for drinking 
water treatment, therefore, investigations about the occurrence of benzotriazoles in the tap 
water will be undertaken in the next chapter. 
TT BT 
 
 
 
 
 
 
 
 
 
Chapter Eight: Results of the Occurrence and Possible 
Source of Benzotriazole and Tolyltriazole in 
Potable Water 
 
 
 
 
 
 
                                                                                                                                                                      Chapter Eight 
 
113 
 
Overview        
To date, around the world, many researchers reported some emerging contaminants in 
drinking water. Therefore this chapter will report the occurrences of benzotriazoles in the 
tap water around Uxbridge, West London. Although these chemicals are widely used in the 
producing of many products and then they might end up to the environment like break 
fluids, motor vehicle antifreeze and aircraft de-icing fluids. However, only one possible 
input (dishwasher detergents) that might contribute in the occurrences of these chemicals 
in the tap water will be described in this chapter.  
                   
8.1 Occurrence in drinking water 
During the study to find the occurrence of benzotriazoles in the tap water, BT and / or TT 
were detected in all tap water samples analysed. Figure 8.1 shows Box plots of 
concentrations of BT and TT in tap water, median concentrations and the 25-75 percentile 
range are shown in the box with whiskers at 5 and 95 percentiles. From the Figure 8.1, it 
can be seen that the concentrations of BT were higher than the concentrations of TT in all 
samples, the opposite of that seen in the river survey. This is probably due to the fact that 
TT is more hydrophobic than BT and the granular activated carbon used in the drinking 
water treatment plant at Iver removed TT more effectively, therefore the TT concentrations 
were lower that BT concentrations. The mean concentration of BT was 30.9 ng/l ranging 
from 0.6 ng/l to 79.4 ng/l. While TT mean concentration was 15.1 ng/l and varied from 0.5 
ng/l to 69.8 ng/l.  The full data are shown in appendix 5. 
Throughout the period of monitoring these chemicals in the drinking water, eight samples 
were collected from the MilliQ water system existed in the laboratory at Brunel University, 
which represented the blank samples which were also analysed. The MilliQ system at 
Brunel consists of carbon pre-cartridge followed by reverse osmosis (RO) and then ion 
exchange and all these three technologies classifies as types of advance water treatment. 
Therefore, the results show that mean concentrations of BT and TT were 1.2 and 0.5 ng/l 
                                                                                                                                                                      Chapter Eight 
 
114 
 
respectively. In addition, 25% and 50% of the values of the blank samples were below the 
limit of quantification (<0.5ng/l) for BT and TT respectively. 
 
Figure 8.1 Box plots of concentrations of BT and TT in tap water. Median 
concentrations and the 25-75 percentile range are shown in the box 
with whiskers at 5 and 95 percentiles. 
In terms of estimating the actual human exposure through the tap water, it is possible that 
taking average concentrations without considering to the spatial distribution might 
mislead. Therefore, Figure 8.2 shows the change in the concentrations of BT represented by 
13 of the 20 locations over a 20 km distance from east to west around Uxbridge, west 
London. The results show that there was a significant difference between the concentration 
of BT in west of and Uxbridge, also there was some evidence of difference between the 
concentrations of BT at Uxbridge and east of it. In addition, the results show that the 
concentrations of BT in the area of 6-9 Km west of Uxbridge were <10 ng/l, while about 1.5 
km around Uxbridge the BT concentrations were between 27.6-58.2 ng/l, and the BT 
concentrations were ranged from 40-80 ng/l at about 11-14 km to the east of Uxbridge. The 
other 7 samples excluded from Figure 8.2, four of them were to the north of Uxbridge, and 
  
B e n zo t r i a z o l e  
C
o
n
ce
n
t
r
a
t
io
n
 
(
n
g
/
L
)
 
0  
20  
40  
60  
80  
1 0 0  
T o l yl t r i a zo l e  
                                                                                                                                                                      Chapter Eight 
 
115 
 
had between 17 and 29 ng/l. The other three samples were from between 40 to 100 km 
distant, with 5 to 25 ng/l BT. 
 
 
Figure 8.2 Change in concentration of BT (     ) and TT (      ) in tap water from 13 of 
20 sampling points, error bars show maximum and minimum 
concentration. 
For tolyltriazole, Figure 8.2 demonstrates also the spatial variation of the TT 
concentrations. Concentrations of <5 ng/l to the west, increased by an order of magnitude 
within 20 km east, where values ranged from 50 to 70 ng/l (Figure 8.2). Locations to the 
east and west of Uxbridge in Figure 8.2 are supplied by Thames Water, and differences in 
concentrations may be attributable to factors such as the source of drinking water supply 
(e.g. groundwater or surface water), treatment processes and mixing in distributions 
systems. Four of the 7 samples excluded from Figure 8.2 were to the north of Uxbridge, and 
had between 5 and 12 ng/l of TT. The other three samples were from between 40 to 100 
km distant, with 1 to 28 ng/l TT. 
The ratio of the BT concentration to TT concentration was different from west to east of 
Uxbridge. It can be seen the ratio of BT/TT within Uxbridge which is served by Veolia was 
different. This is probably because of the GAC system existed in the water treatment plant 
0 
10 
20 
30 
40 
50 
60 
70 
80 
6-9 km west of Uxbridge Samples from within 1.5 km 
of Uxbridge 
7-11 km east of Uxbridge 
Co
nc
ent
rati
on 
ng
/l 
                                                                                                                                                                      Chapter Eight 
 
116 
 
that served Uxbridge.  The GAC process adsorbed the TT because it is more hydrophobic 
and therefore, the removal of TT was higher than BT. It is possible that there were no, or 
limited, GAC systems in water treatment plants supplying areas to the east and west of 
Uxbridge and therefore the ratio of BT to TT was different.  
8.2 Estimation of the inputs of BT and TT from dishwasher 
detergents 
The analysis of dishwasher powders and tablets confirmed the presence of either BT or TT 
in all products (Table 8.1). The range of amount was between minimum of 0.5 mg per 20 g 
in one own brand tablet to 60 mg in a leading brand tablet product. In order to calculate the 
average load of BT and TT, market share information was used and use pattern also (Mintel 
International, 2009a; Mintel International, 2009b). To estimate how many washes were 
undertaken per day, we used the population equivalent of Hallam Fields, one of the eight 
the STWs on the River Erewash (44,895), assuming 2.36 people per household (The Office 
for National Statistics, 2003) to derive 19,023 households. With dishwasher ownership of 
28% (Waterwise, 2008), this gave 5,326 households with dishwashers. One wash per day 
was assumed in each household. According to these information and assumption, the 
average load per wash was 1.45 mg of BT and 27.8 mg of TT as illustrated in Table 8.1. With 
an assumption of one use per household per day, this resulted in estimated inputs of 7.72 g 
of BT (5,326 x 1.45 mg) and 148 g of TT (5,326 x 27.8 mg) per day to this particular STW 
(Table 8.1). With a flow of 10 Ml/day, the estimate of concentrations in the influent at the 
STW was 772 ng/l BT and 14,800 ng/l TT. 
The average concentrations in the effluent from the primary settling tanks (settled sewage) 
at Hallam Fields during four days in November 2008 were 2,482 ng/l of BT and 3,271 ng/l 
TT. It is apparent that the exercise underestimated the measured load of BT, and 
overestimated that of TT assuming minimal removal in primary treatment. As only one 
branded product contained TT, then the relative inputs of BT and TT from dishwasher 
detergents will depend very much on market share of that brand and on the proportion of 
people who use the tablet form of that brand. Given the assumptions made in calculating 
inputs, and possible limitations of the limited sampling regime in assessing true inputs, it 
                                                                                                                                                                      Chapter Eight 
 
117 
 
would appear that the use of these chemicals in dishwasher formulations may account for a 
significant proportion (at least 30%) of the inputs to the STW and subsequently the 
environment. To further improve this estimate, more accurate, catchment specific data on 
sales and use of dishwasher detergents and also looking at the use of detergents at 
restaurants and catering places such as hospitals and universities would be required, along 
with a more comprehensive sampling strategy at the STW. A full source apportionment 
exercise has not been undertaken; and other uses, such as in corrosion inhibitors for 
heating systems and motor vehicles could also contribute to the load to sewer, however the 
estimation has highlighted that the use of BT and TT in “down the drain” products may 
make a significant contribution to their concentrations in UK rivers. Appendix 5 contains all 
original date for benzotriazoles in drinking water samples and data analysis of dishwasher 
detergents. 
Summary 
Benzotriazole and TT were found in ng/l in drinking water samples, TT concentrations 
were lower than BT concentration due to its hydrophobicity. Dishwasher detergents as a 
one possible source of their occurrence in the aquatic environment was estimated and 
many factors need to be covered in order to improve this estimation. 
 
 
 
 
 
 
 
                                                                                                                                                                      Chapter Eight 
 
118 
 
Table 8.1 Amount of BT and TT present in dishwasher detergent products from 
UK supermarkets (mg per 20g of tablet or powder). 
  Load in 20 g 
of product 
(mg) 
Weighted 
loada 
(mg) 
Market 
share 
(%) 
Load per 
washb 
(mg) 
 Type BT TT BT TT  BT TT 
Finish tablet  60.0  51.4 54  27.8 
 powder  17.0      
Fairy tabletc 4.5  4.5  17 0.77  
Sainsbury's tablet 0.9  3.9  5.4d 0.21  
 powder 16.0       
Morrison tablet 0.5  3.8  4.0d 0.15  
 powder 17.0       
Asda tablet 1.3  1.5  5.8d 0.09  
 powder 2.3       
Tesco tabletc 2.2  2.2  10.8d 0.24  
Total market share     97.0   
Average load per washe     1.45 27.8 
 
a calculated based on 80% of people using the tablet formulation. = (mg in tablet x 0.8) + (mg in 
powder x 0.2) 
b calculated by taking into account the market share of the product = weighted load/100*market 
share 
c These products were only available in tablet form 
d Market share of these products was assumed to be the same as the market share of food sold by 
the four major UK supermarkets (Mintel International, 2009b) 
e Summing of load per wash gives an estimated input per wash based on the amount in each product 
and use of that product 
 
 
 
 
 
 
 
 
 
 
Chapter Nine: Discussion 
 
 
 
 
 
 
 
 
                                                                                                                                                                       Chapter Nine 
 
120 
 
9.1 Occurrence and removal of emerging contaminants in 
conventional treatment 
       
The research has shown that both the trickling filter and activated sludge process were 
effective at removing sanitary parameters (SS, BOD and ammonia). The data have also 
shown that there was little difference in the effectiveness of the two STWs, which may have 
been a consequence of the sampling regime that was used. 
      
9.1.1 Progestogens. 
Of the 10 progestogens covered in this study, only 8 appear to have been reported by other 
workers (CPA, DSP, MDP, MPA, MTA, NGL, NTD and PGT). Some compounds analysed in this 
present study, such as tibolone and dydrogesterone appear not to have been determined by 
other workers. Two of the compounds of interest have been reported in only single studies; 
in the case of cyproterone acetate by Sun et al. (2009), where CPA was not detected in the 
influent or effluent of a STW, and drosprinone was also reported as not detected (Vulliet et 
al., 2008). However the natural hormone, progesterone, has been observed by a number of 
workers. There are about 30 studies, since 2002, which have reported the occurrence and 
removal of progestogens in the aquatic environment. A review of these studies is listed in 
Table 9.1.  
 In this study, progesterone (PGT), the natural hormone, was the predominant compound 
and was detected and quantified in all samples of the influent with a concentration of 46.9 ± 
30.6 ng/l and 41.6 ± 14.5 ng/l at both STWs. Similar findings were also reported by other 
studies that have shown that PGT was the most frequently detected compound but with 
surface waters not wastewaters (Vulliet et al., 2008; Chang, Wan & Hu, 2009). In addition, 
other studies showed that PGT was the predominant compound and the mean 
concentrations of PGT were compatible with the findings achieved in this study,  33.1 ± 8 
ng/l (Fan et al., 2011)  and 66 ± 36 ng/l (Chang et al., 2011). In contrast, other results have 
shown that norgestrel (NGL) was the predominant compound with 59.0 ± 28.3 ng/l (Liu et 
al., 2011), although PGT (4.1- 6.4 ng/l) was also observed in their study. This concentration 
of NGL was in agreement with our findings of 23 ± 7.5 ng/l, however, the high standard 
                                                                                                                                                                       Chapter Nine 
 
121 
 
deviations, and range of concentrations reported for these compounds (Table 9.1) highlight 
the uncertainty in reported values. 
Progestogens are not the only steroids hormones studied in the waters and wastewaters. 
There are some studies which have demonstrated that androgens were the most 
predominant chemicals among the steroids hormones (Fan et al., 2011; Chang et al., 2011), 
followed either by the estrogens as the second contributor (Fan et al., 2011) or 
progestogens (Chang et al., 2011). Therefore more investigations are required to clarify the 
predominant chemicals in contrast to other hormones in particular as more progestogens 
are used in the hormonal medicine (factor of 3-100) than estrogens (Zeilinger et al., 2009). 
The concentrations of progestogens in the final effluent of the STW measured by other 
studies are also listed in the Table 9.1. The overall removal efficiencies of progesterone in 
the two STWs studied in this study were 96% and 97% which is in agreement with other 
published work when they demonstrated that the removal efficiency achieved in two STW 
were 90% and 96% (Chang et al., 2008). In addition, synthetic progestogens, norgestrel 
(NGL) removed at a percentage of 89% (Qiao et al., 2009), while in our finding this was 76% 
and 92% at Hallam Fields and Newthorpe STWs respectively. 
The present study has shown also that the synthetic progestogens were slower to be 
removed than the natural progestogen (PGT) in conventional biological treatment. 
Estrogens are an example of where the synthetic compound degrades more slowly when 
more than 98% of the natural hormones (E1+E2) were removed while 90% of EE2 was 
removed (Andersen et al., 2003).  This finding is supported by the studies achieved by Joss 
et al. (2004), Shi et al. (2004) and Esperanza et al. (2007), to understand the behaviour of 
natural and synthetic estrogens when estrone (E1), 17β-estradiol (E2), and estradiol (E3) 
were more easily degraded than the synthetic estrogen 17α-ethinylestradiol (EE2), even 
though lower removal for (E1) had occurred due to the transformation of (E2) and (E3) to 
(E1). However, there is only one synthetic estrogen of significance (EE2) and there are 
many synthetic progestogens. 
Removal of chemicals during biological treatment can be achieved either by degradation or 
sorption, and subsequent removal with the solids. In relation to degradation, given the 
nature of process, much focus is on the biological degradation, and chemical degradation is 
not usually considered as significant. Although it was not feasible to find out whether 
                                                                                                                                                                       Chapter Nine 
 
122 
 
progestogens undergo degradation or sorption during the biological treatment, however 
there is some evidence that the role of sorption process in removing steroids during the 
wastewater treatment is less significant than biodegradation even with the more 
hydrophobic compounds (Gomes et al., 2011), and other study also demonstrated that PGT 
does not partition to solids (Esperanza et al., 2007). Additionally, no significant removal had 
occurred when mercury chloride HgCl2 was added to the sample in order to inhibit the 
biological activity (Chang et al., 2011). Furthermore, in our findings, there was no link 
between the log Kow and removal of compounds during the biological treatment. This 
implies that most of PGT may have been removed via biodegradation and in our findings; 
N/AS and trickling filter were able to remove 92% and 90% of the PGT respectively. 
Therefore, it is likely that PGT degraded rapidly during the biological treatment and other 
studies support that observation (Esperanza et al., 2004; Labadie & Budzinski, 2005b). 
Conversely, Fan et al. (2011), demonstrated that no significant removal had occurred 
through the aerobic tank in their study at a nutrient removal plant (BNR) and that was 
probably due to the low initial concentration of PGT (4.5 ± 1.6 ng/l) at the influent of the 
aeration tank of their study as it had already degraded in the anoxic and anaerobic section 
of the nutrient removal plant.  
                                                                                                                                                                                                                                                 Chapter Nine 
 
123 
 
Table 9.1  Occurrences of progestogens in the aquatic environment (ng/l) 
 
Chemical 
Surface 
water 
Ground 
water 
Drinking 
water STW References 
(ng/l) (ng/l) (ng/l) 
        Influent (ng/l) Effluent (ng/l)   
MDP 0.4 – 1 N.D     Max. 15 (Kolodziej, Harter & Sedlak, 2004; Kolodziej & Sedlak, 2007) 
  N.D          (Zheng, Yates & Bradford, 2008) 
  N.D N.D        (Vulliet et al., 2008) 
  N.D   N.D   N.D  (Sun et al., 2009) 
        N.D N.D (Liu et al., 2011) 
MPA N.D     0.21- 4.42 0.03 – 0.42 (Chang et al., 2008) 
  0.04 – 34        N.D (Chang, Wan & Hu, 2009) 
        1.08 ± 0.1 0.06 ± 0.03 (Fan et al., 2011) 
  N.D – 1.4     18 -58 N.D – 1.1 (Chang et al., 2011) 
MTA N.D       0.35 (Chang et al., 2008) 
  0.23 – 25        N.D (Chang, Wan & Hu, 2009) 
  N.D         (Sun et al., 2009) 
        4.6 ± 4 0.2 ± 0.06 (Fan et al., 2011) 
        1.9 – 9.3 N.D – 0.7 (Chang et al., 2011) 
NTD       N.D – 8.9 N.D – 17.4 (Petrovic et al., 2002) 
  < 872         (Kolpin et al., 2002) 
  N.D       N.D (Labadie & Budzinski, 2005a; Labadie & Budzinski, 2005b) 
 
                                                                                                                                                                                                                                                 Chapter Nine 
 
124 
 
Table 9.1  Continued 
 
Chemical 
Surface 
water 
Ground 
water 
Drinking 
water STW References 
(ng/l) (ng/l) (ng/l) 
        Influent (ng/l) Effluent (ng/l)   
 NTD         5.2 - 41 (Vulliet et al., 2007) 
  N.D   N.D   N.D (Kuster et al., 2008; Sun et al., 2009) 
  2.7  &  2.8 4.2 – 5.6       (Vulliet et al., 2008) 
  N.D     N.D N.D (Chang et al., 2008) 
  N.D       N.D (Kuster et al., 2009) 
  N.D – 16       N.D (Chang, Wan & Hu, 2009) 
  N.D         (Velicu & Suri, 2009; Kuster et al., 2010) 
        N.D N.D (Fan et al., 2011) 
  N.D     5.3 – 12 N.D (Chang et al., 2011) 
  N.D     N.D N.D (Liu et al., 2011) 
NGL        N.D - 16.1 N.D - 4 (Petrovic et al., 2002) 
  N.D       N.D (Labadie & Budzinski, 2005a; Labadie & Budzinski, 2005b) 
          0.9 – 17.9 (Vulliet et al., 2007) 
  N.D   N.D   N.D (Kuster et al., 2008; Sun et al., 2009) 
  5.3 & 7 7.4 – 11       (Vulliet et al., 2008) 
  N.D     N.D N.D (Chang et al., 2008) 
        5.6 1.1 (Pu et al., 2008) 
  N.D       N.D (Kuster et al., 2009) 
 
                                                                                                                                                                                                                                                 Chapter Nine 
 
125 
 
Table 9.1  Continued 
 
Chemical 
Surface 
water 
Ground 
water 
Drinking 
water STW References 
(ng/l) (ng/l) (ng/l) 
        Influent (ng/l) Effluent (ng/l)   
 NGL 6.2       N.D (Chang, Wan & Hu, 2009) 
  7.5   N.D 74.3 8.1 (Qiao et al., 2009) 
  N.D         (Velicu & Suri, 2009; Kuster et al., 2010) 
  N.D       N.D (Fan et al., 2011) 
  N.D     N.D N.D (Chang et al., 2011) 
PGT 6   6     (Aherne, English & Marks, 1985) 
        N.D – 1.9 N.D – 1.5 (Petrovic et al., 2002) 
  199          (Kolpin et al., 2002) 
  14 – 44         (Vanderford et al., 2003) 
  N.D N.D       (Kolodziej, Harter & Sedlak, 2004) 
  N.D       N.D (Labadie & Budzinski, 2005a; Labadie & Budzinski, 2005b) 
          8 – 16.9 (Vulliet et al., 2007) 
  1.4 – 4.2       2.1 (Kolok et al., 2007) 
   Max. 27       N.D (Kolodziej & Sedlak, 2007) 
  0.32 – 1.39   0.93     (Kuster et al., 2008) 
  N.D         (Zheng, Yates & Bradford, 2008) 
        4.3 - >100 N.D – 3.2 (Pauwels et al., 2008) 
  4.5 ±1.7       0.78 & 0.86 (Van der Linden et al., 2008) 
 
                                                                                                                                                                                                                                                 Chapter Nine 
 
126 
 
Table 9.1  Continued 
 
Chemical 
Surface 
water 
Ground 
water 
Drinking 
water STW References 
(ng/l) (ng/l) (ng/l) 
        Influent (ng/l) Effluent (ng/l)   
 PGT 1.7 & 3.5 2.5 – 4.1       (Vulliet et al., 2008) 
  0.06 – 0.09     3.1 & 10 0.31 & 0.37 (Chang et al., 2008) 
  0.72 – 6.5         (Standley et al., 2008) 
  0.51 – 47.2         (Kuster et al., 2009) 
  N.D – 26       0.48 – 1.4 (Chang, Wan & Hu, 2009) 
  Max. 3.1   Max. 0.57     (Benotti & Brownawell, 2009) 
  7.35 – 1.8         (Velicu & Suri, 2009) 
  N.D   N.D   N.D (Sun et al., 2009) 
          N.D (Mnif et al., 2010) 
  N.D         (Kuster et al., 2010; Yoon et al., 2010; Singh et al., 2010) 
      N.D     (Sodre, Locatelli & Jardim, 2010) 
        6.62 0.99 (Fan et al., 2011) 
  N.D – 1.7     35 - 108 0.8 – 2.3 (Chang et al., 2011) 
  0.5-2.5     5.4 & 6.1 N.D (Liu et al., 2011) 
 
N.D: not detected 
 
                                                                                                                                                                       Chapter Nine 
 
127 
 
9.1.2 Benzotriazoles 
Both benzotriazole and tolyltriazole have been reported to be ubiquitous in many European 
countries, and the concentrations of BT and TT reported in the aquatic environment are 
listed in Table 9.2. The concentrations of benzotriazoles in the influent STW were much 
higher than the progestogens group. This is because they are produced in high volume 
(HPV) and widely used as anti corrosives, in cooling and hydraulic fluids, in aircraft de-icing 
fluids, and in the formulation of dishwashing detergents (Hart et al., 2004). In our findings, 
the concentrations of BT (2.3-2.4 μg/l) in the influent was lower than reported by Weiss & 
Reemtsma (2005) and higher than of that Jover, Matamoros and Bayona (2009). A possible 
explanation for this might be that this difference is due to the difference in using these 
chemicals in formulations of products and patterns of use in different countries. In terms of 
TT, the concentrations of total TT were relatively similar to those reported in Germany 
(Weiss & Reemtsma, 2005).  
In the biological treatment, BT and TT were partially removed. Other studies corroborated 
that when they observed that biological treatment was not able to remove these 
compounds completely (Voutsa et al., 2006; Reemtsma et al., 2006; Giger, Schaffner & 
Kohler, 2006). The removal efficiency of biological treatment was in the range of 28% - 
39% for both chemicals at both STWs. This finding is in agreement with other studies, such 
as Weiss, Jakobs and Reemtsma (2006) when 37% of BT was removed. The 
physicochemical properties of this group has an important role in terms of their fate and 
occurrence in the wastewater, whereas low log Kow (1.59 ± 0.23) for benzotriazoles, high 
degree of solubility and polarity in water and this means that BT and TT are difficult to get 
removed by sorption during conventional treatment. Furthermore, BT and TT are resistant 
to biodegradation (Voutsa et al., 2006; Giger, Schaffner & Kohler, 2006) and this is also a 
factor that affects their removal during conventional biological treatment. 
                                                                                                                                                                                                                                                 Chapter Nine 
 
128 
 
Table 9.2  Occurrences of benzotriazoles in the aquatic environment (μg/l). 
 
Chemical Surface water Ground water STW References 
  (μg/l) (μg/l) Influent (μg/l) Effluent (μg/l)   
BT           
  3.4 N.D 11.9 ± 1.2 9.6 ± 1.3 (Weiss & Reemtsma, 2005) 
  1 (Max = 6.3)       (Giger, Schaffner & Kohler, 2006) 
  0.175-1.2 (lake)       (Giger, Schaffner & Kohler, 2006) 
  0.636 – 3.690   13 - 75 11 - 100 (Voutsa et al., 2006) 
  2.7   12 7.7 (Weiss, Jakobs & Reemtsma, 2006) 
  0.6     7.3 (Reemtsma et al., 2006) 
        8 (van Leerdam et al., 2009) 
  0.493       (Loos et al., 2009) 
  0.213       (Loos, Locoro & Contini, 2010) 
  N.D - 0.68     7.0-18 (Reemtsma et al., 2010) 
  0.24   0.131 0.129 (Jover, Matamoros &  Bayona, 2009) 
  0.038 - 1.474       (Kiss & Fries, 2009) 
    0.024 (Max=1.032)     (Loos et al., 2010) 
 TT  
  2.4       (Kolpin et al., 2002)  
† 0.2 N.D 2.5 ± 2.6 2.2 ± 1.6 (Weiss & Reemtsma, 2005) 
‡ 0.1 N.D 2.0 ± 2 .0 2.1 ± 1.3 (Weiss & Reemtsma, 2005) 
 
 
 
                                                                                                                                                                                                                                                 Chapter Nine 
 
129 
 
Table 9.2 Continued 
Chemical Surface water Ground water STW References 
  (μg/l) (μg/l) Influent (μg/l) Effluent (μg/l)   
  0.2 (0.04 - 0.47)       (Giger, Schaffner & Kohler, 2006) 
  0.03 - 0.23 (lake)       (Giger, Schaffner & Kohler, 2006)  
  0.122 – 0.628   0.2 - 5.6 0.1 - 3.8 (Voutsa et al., 2006) 
† 0.2   1.3 1.2 (Weiss, Jakobs & Reemtsma, 2006) 
‡ 1.2   2.1 2.1 (Weiss, Jakobs & Reemtsma, 2006) 
  0.2     2.2 (Reemtsma et al., 2006) 
        3 (van Leerdam et al., 2009) 
  0.617       (Loos et al., 2009) 
  0.081       (Loos, Locoro & Contini, 2010) 
† N.D - 0.13     0.8 - 1.2 (Reemtsma et al., 2010) 
‡ 0.2 - 0.46     1.0 - 5.0 (Reemtsma et al., 2010) 
† N.D - 2.16       (Corsi et al., 2003) 
‡ N.D - 1.67       (Corsi et al., 2003) 
† 0.925   N.D N.D (Jover, Matamoros & Bayona, 2009) 
‡ 1.561   N.D N.D (Jover, Matamoros & Bayona, 2009) 
† 0.25 - 0.281       (Kiss & Fries, 2009) 
    0.02 (Max= 0.516)     (Loos et al., 2010) 
† For 5- isomer TT  ‡ For 4- isomer TT 
                                                                                                                                                                       Chapter Nine 
 
130 
 
9.1.3 The mechanism of removal of emerging contaminants 
during wastewater treatment. 
The main removal mechanism during the biological treatment has been reported to be 
biodegradation (Daughton & Ternes, 1999; Onesios, Yu & Bouwer, 2009). Although 
suspended growth process (activated sludge process) has demonstrated better removal 
than attached growth like trickling filter for many emerging contaminants (Svenson, Allard 
& Ek, 2003; Janex-Habibi et al., 2009; Limpiyakorn, Homklin & Ong, 2011). It also been 
noted that a nitrifying process is more able to remove ECs than other steps, since Anderson, 
Suarez and their co- workers have demonstrated that most of the natural estrogens 
(E1+E2) were largely biodegraded during the aerobic and anoxic stages, while the synthetic 
17α-ethinylestradiol (EE2) was less biodegraded in the anoxic stage (Andersen et al., 2003; 
Suarez, Lema & Omil, 2010). However this present study did not clearly demonstrate that 
the ASP was better to remove them than the TF and this maybe a result of factors such as 
sampling/analytical issues related to the relatively small sample numbers and low 
concentrations, close to LOQ for the progestogens. 
The removal efficiency for emerging contaminants varies from compound to compound. 
There is also broad variation in the removal efficiency for the same compound in different 
STWs. This implies that many parameters have influenced this removal rate and several 
studies have investigated these factors (Clara et al., 2005b; Radjenovic, Petrovic & Barcelo, 
2007; Koh et al., 2008; Cirja et al., 2008).  The physicochemical properties of the chemicals 
by means of hydrophobicity and hydrophilicity; operational conditions, such as sludge 
retention time (SRT), hydraulic retention time (HRT); and effluent characteristics like 
temperature, pH, and flow rate have been investigated and they have affected the removal 
efficiency of ECs during the conventional treatment. For example, longer SRT allow growing 
a more diverse bacterial population (including nitrifying bacteria) and that provides a wide 
spectrum of microorganisms that have the ability to metabolize the target compounds and 
consequently improve the removal efficiency ( Johnson & Sumpter, 2001; Clara et al., 
2005a; Koh et al., 2008;). Also increasing the HRT allows increased contact time and more 
time for biodegradation and adsorption leading to enhanced removal efficiency (Kirk et al., 
2002; Svenson, Allard & Ek, 2003). Therefore high HRT and SRT are essential for high 
                                                                                                                                                                       Chapter Nine 
 
131 
 
removal rate (Miege et al., 2008). Temperature also has an influence on the removal of 
compounds, as noted when high concentrations of compounds were observed in effluent 
during winter compare to summer (Vieno, Tuhkanen & Kronberg, 2005). 
It is important to understand how to remove these chemicals from wastewater as they may 
have an environmental impact, and although it can be considered that removal of 90% and 
above may be “good”, this may not be sufficient to protect the environment. It is therefore 
worth considering at what concentrations they may be of concern. 
 
9.1.4 The possible significance of these compounds in the 
environment 
The effects of target compounds are not completely clear yet, although there are some 
studies which  stated that at such levels of progesterone (maximum 1.39 ng/l) is considered 
not to pose a risk to human toxicity (Kuster et al., 2008). Moreover, medroxyprogesterone 
showed no or little effect (up to 5 mg/l) on aquatic organisms (Ceriodaphnia dubia) 
(Jukosky, Watzin & Leiter, 2008). However, there is some evidence of the possible impact of 
some of the chemicals of interest on wildlife and humans, for example, norethindrone 
showed a significant decrease in fecundity of fathead minnow at low level (1.2 ng/l) (Paulos 
et al., 2010). Additionally, there is some evidence of the impact of some of these, such as 
norgestrel and drosprinone have on the aquatic organisms; hence it was found that low 
ng/l range (3.3 ng/l for NGL, and 6.5 µg/l for DSP) exhibited an inhibition to the 
reproductive function in adult fathead minnows (Zeilinger et al., 2009). Although the mean 
effluent concentration of NGL at Hallam Fields STW was higher than 3.3 ng/l, however, the 
dilution rate of effluent in the river is an important factor to know whether this compound 
may have an impact on the aquatic organisms. Cyproterone acetate has been observed to 
exhibit an antiandrogenic activity (three times more than drosprinone) by preventing the 
androgen receptor from androgen binding (Fuhrmann et al., 1996). 
The other group of interest, benzotriazoles, has been noted as toxic to aquatic organisms 
(Cornell, Pillard & Hernandez, 2000), and therefore may cause adverse effect in the aquatic 
                                                                                                                                                                       Chapter Nine 
 
132 
 
environment. Although benzotriazole (BT) is less toxic than TT (Pillard et al., 2001), 
however BT at 32 mg/l can  interfere  with  the  regulation  of  embryo development  in  
protochordates such  as  Ciona  intestinalis (Kadar, Dashfield & Hutchinson, 2010). 
Moreover, the Dutch Expert Committee for Occupational Standards concluded that there 
are some studies with rat and mice which demonstrated that BT may be carcinogenic 
(DECOS, 2000). In addition, Zhang et al. (2008) found that BT derivatives are able to induce 
growth inhibition in cancer cells and benzotriazole had an antiestrogenic activity in vitro 
but not in vivo (Harris et al., 2007). Limited chronic and acute ecological toxicity data 
indicate that BT is moderately toxic to Lepomis macrochirus (96-h LC50 =31 mg/l) and 
Daphnia magna (48-h LC50 = 74 mg/l) (Cornell, Pillard & Hernandez, 2000). It is therefore 
possible that such connections may exist between benzotriazoles and some impact on 
wildlife and aquatic organisms. 
When discharged to the environment, there is frequently dilution of effluents in receiving 
waters which reduces the concentrations of the individual chemicals. However, groups of 
chemicals, such as the progestogens, may, if their effects are additive, still be of concern. 
Evidence for such effects was seen in a mixture of five similarly-acting chemicals: all were 
estrogens, even though one was a pharmaceutical, one a natural hormone, and three 
industrial chemicals was tested and they found that these chemicals acted in an additive 
manner, meaning that the effect of each chemical could be added together, and if the 
chemicals in a mixture all act in the same way, the effects will be additive (Brian et al., 
2005). Additionally, their effects were not antagonistic or synergistic. In this study, the total 
concentrations of progestogens that discharged to the surface waters from the STWs were 
32.1 ng/l and 16 ng/l for Hallam Fields and Newthorpe STWs respectively and the total 
concentrations of progestogens (natural and synthetic) along the River Erewash ranged 
from 10.9 ng/l to 27.0 ng/l. These progestogens were present in the same river sample and 
this would suggest that their effects would be additive assuming they are equally potent. 
Therefore to understand the threat, to wildlife or human health, a greater understanding of 
the risk posed by these very complex mixtures of chemicals is required. 
In general, the concentrations of benzotriazoles were much higher in influent and effluent 
than progestogens. The activated sludge process and trickling filter considered in this study 
                                                                                                                                                                       Chapter Nine 
 
133 
 
have the ability to reduce the concentrations of emerging contaminants in wastewater but 
not to eliminate them completely. The concentrations of target compounds were lower in 
the effluent than those in the influent and that would suggest that biodegradation and 
sorption take place during STW. Conventional biological treatment, perhaps by chance, 
does remove amounts of a range of emerging contaminants. But although this can be more 
than 90% for some compounds, there are some other compounds poorly removed and this 
implies that there is a wide variation in their removal efficiency due to the differences in the 
physicochemical properties of each compound and also types of operation in addition to its 
operation parameters. According to these impacts, it seems that there is no emerging 
concern about BT and TT although there is no confirmed evidence about their action as a 
carcinogen (EPA, 2011). While for progestogens, there is some evidence that they may 
cause a problem with low ng/l. Thus, although conventional treatment removes “well”, it 
may not be enough and therefore more treatment might be needed. 
 
9.2 Occurrence and removal of emerging contaminants 
during advanced treatment 
 
As previously explained that conventional treatment was designed to remove the 
conventional contaminants represented by the organic materials (BOD/COD) and 
suspended solids and in some of them were also designed to remove ammonia. Moreover, 
in this study and many other studies documented that conventional treatment only partially 
removes the emerging contaminants. In the results chapters, the sand filters used at Hallam 
Fields and Newthorpe STWs were included in the assessment of “conventional treatment”. 
However, here they are considered as a tertiary treatment, because they are relatively low- 
energy that may enhance the removal of a range of chemicals. 
   
 
 
                                                                                                                                                                       Chapter Nine 
 
134 
 
Sand Filter 
Although sand filter was not designed to remove emerging contaminants from wastewater, 
however, removal of progestogens and benzotriazoles did occur in this study with removal 
efficiency rate from 53 - 94% in trickling filter STW and from no removal to 62% at the 
activated sludge STW.  In addition, the sand filter at Hallam Fields STW was able to remove 
14% and 26% of BT and TT respectively and 61% was removed for BT and TT during the 
sand filter at Newthorpe STW.  Therefore the performance of the sand filter at the TF plant 
appeared better than that one of ASP sewage work although there was no significant 
difference. There is very limited information available to demonstrate the performance of 
sand filter in terms of removing emerging contaminants from wastewaters. However, the 
results achieved by Gunnarsson et al. (2009) exhibited that estrone (E1) and bisphenol A 
(PBA) had reduced from 6.3 ng/l to 0.67 ng/l and from 780 ng/l to 420 ng/l respectively 
due to the fact that the sand filter demonstrated biological activity (nitrification). 
 
Ozone (O3) 
 The removal rates of progestogens (natural and synthetic) by using ozone in this study 
were relatively low ranging from (0 – 59%). Limited information is available about the 
removal of progestogens in the literature to compare with.  There are many factors that 
might influence the removal rate of these chemicals such as the structure of target chemical, 
dose of ozone and contact time, initial concentration of the target compound and the quality 
of wastewater.  Westerhoff et al. (2005) found that the steroids containing phenolic 
moieties such as estradiol, ethynylestradiol, or estrone are oxidised more efficiently than 
those without aromatic or phenolic moieties like progesterone and testosterone. This is 
supported by Broseus et al. (2009) when they found in drinking water (not wastewater) 
samples that  many progestogens (natural and synthetic) were far slower to react with 
ozone compare to estrogens although progesterone was detected in one sample before 
ozonation and was not detected after. Another study confirmed that when similar 
conditions were applied for river water samples, the removal efficiencies of estrogens were 
higher than progesterone (Snyder et al., 2006).  
Our study was not able to test the ozone dose, as it was arranged around other work at 
Hallam Fields.  The applied dose of ozone used in present study during the treatment was 
                                                                                                                                                                       Chapter Nine 
 
135 
 
1mg O3 /l with 3 minutes contact time which was close to another study by Snyder et al. 
(2006), when they found that with 2.4 mg O3/l, the removal efficiency for progesterone 
differed at 2 and 6 minute contact time. Other studies suggest that 10mg O3 /l with 40 
minutes could achieve a high removal for PPCPs (Gabet-Giraud et al., 2010).  In general, the 
applied dose at Hallam Fields was relatively lower than what other studies recommended, 
with O3 doses ranging from 5 – 15 mg/l and contact time of about 15–30 minutes (Ternes et 
al., 2003; Verlicchi et al., 2010). Therefore, this factor probably affected the removal 
efficiency for progestogens, which is corroborated by reported estrogen removal at Hallam 
Fields which was relatively low (60-70%) when compared to other studies (Filby et al., 
2010).  
The initial concentration of the target compounds (pre - ozonation) plays an important role 
in measuring the removal efficiency, as when the initial concentration was very low or just 
above the limit of quantification, then it was difficult to find out how much was degraded or 
decomposed and consequently quantification of these chemicals resulted from an analytical 
variations rather than an actual concentration variation (Reungoat et al., 2010). Therefore 
to determine removal rates accurately at very low concentrations (< 5ng/l), sensitive and 
precise analytical methods are needed to reduce analytical uncertainty. 
For benzotriazoles concentrations were high in relation to LOQ and the present findings 
seem to be consistent with other research which found that 70% of BT (Hollender et al., 
2009) was removed with about 0.6 g O3/ g DOC and at Hallam Fields 73% of BT was 
eliminated. Although Weiss, Jakobs and Reemtsma (2006) found that with 1 mg O3 / mg 
DOC , more than 99% of benzotriazoles were removed, at Hallam Fields it was less with 
between 73 and 79% removal efficiency for BT and TT respectively with the same dose. The 
physicochemical properties of the compounds and the quality of the effluent have an 
influence on the oxidation process. Huber et al. (2005a), showed that ozone reacts readily 
with soluble compounds (such as BT and TT), which will be oxidized a more rapidly than 
compounds sorbed to particles due to limitation of reaction rates by diffusion.  
 
Granular activated carbon (GAC) 
The removal efficiency of GAC for progestogens appeared higher than using ozone however 
there was no significant difference in the post GAC and O3 effluent apart from cyproterone 
                                                                                                                                                                       Chapter Nine 
 
136 
 
acetate (CPA). The effectiveness of GAC corroborates the observations of Rossner, Snyder 
and Knappe (2009), when they suggested that antimicrobial compounds, EDCs and other 
pharmaceuticals can be effectively removed via activated carbon adsorption processes. 
Although Fukuhara et al. (2006), found that adsorption of E1 onto activated carbon was 
higher than E2 due to differences in hydrophobicity, however, our study has been unable to 
demonstrate differences in removal of progestogens with different log kow. A possible 
explanation for this might be that due the low initial concentrations of progestogens and 
also the relatively similar log Kow for the progestogens (3.29 - 3.87).  
In terms of benzotriazoles, 90% and 98% of BT and TT were removed via GAC. The removal 
achieved via GAC for benzotriazoles was higher than for progestogens. However the high 
initial concentration of benzotriazoles (517 ng/l and 2,253 ng/l for BT and TT respectively) 
compared with low nanograms per litre range (< 7 ng/l) as a maximum initial 
concentration of progestogens could have affected the determination of removal rate. The 
main mechanism in removing these chemicals is sorption. The virgin GAC has been proved 
to be more efficient to remove hormones than the reactivated one (Rowsell et al., 2009). 
These workers conducted rapid, small-scale column tests and they found that 81% or more 
of estrogens were removed with the virgin GAC while around 65% were removed with 
reactivated carbon. However, the adsorption capacity is significantly reduced by the 
presence of natural organic matter (Fukuhara et al., 2006). When comparing O3 and GAC, it 
is worth considering that ozone may result in degradation products while GAC removes the 
compounds by adsorption. 
 
Chlorine dioxide (ClO2) 
The behaviour of ClO2 against progestogens and benzotriazoles was similar to ozone 
treatment. Again in our findings, because of the low initial concentrations of progestogens, 
it was difficult to understand the performance of ClO2 towards these chemicals. Although 
Filby et al. (2010), found that ClO2 had the greatest removal effect of estrogens, however a 
study by Deborde et al. (2004), revealed that progesterone remained unchanged and did 
not react with chlorine while all other chemicals which have a phenolic group in their 
structure in their study were rapidly oxidized. Chlorination may also result in degradation 
products. 
                                                                                                                                                                       Chapter Nine 
 
137 
 
The total concentrations of progestogens discharged from the three advanced processes 
(O3, GAC, and ClO2) at Hallam Fields STW were 28.8 ng/l, 18.2 ng/l and 14.0 ng/l 
respectively. While for benzotriazoles these were 603, 101 and 609 ng/l respectively. 
Combinations of different types of advanced technologies may improve the effluent quality 
and that approach was recommended by Snyder et al. (2007) and Verlicchi et al. (2010) , 
when they found that reverse osmosis and advanced oxidation could remove many ECs and 
PPCPs. Additionally, the dilution rates of discharges within the receiving waters play an 
important role in the behaviour of these chemicals against the aquatic organisms. In 
addition, the degradation products produced during ozonation and chlorination of 
progestogens and benzotriazoles were not investigated in this study. In order to identify 
and understand their fate in advanced treatment and the toxicological impacts due to the 
formation of these degradation products, future studies and investigations would be 
required.       
 
9.3 Is there a need to further remove emerging 
contaminants from effluents? 
Progestogens and benzotriazoles are only partially removed during the STWs processes 
and this results in the presence of these compounds in the surface water. The dilution rate 
between the effluents and the river water and different half lives for target compounds, for 
example progesterone (PGT) and cyproterone acetate, this would suggest that different 
levels of concentrations in the river are expected. As mentioned before (section 9.1.1) there 
are some progestogens (cyproterone acetate, drosprinone, dydrogesterone, and tibolone) 
that have not been, or only on one occasion, studied or reported in the aquatic environment. 
However the other chemicals that were observed are in accordance with the concentrations 
observed in this study. The concentrations of medroxyprogesterone (MDP) in the Erewash 
River in this study (<0.4 – 0.6) ng/l was in agreement with Kolodziej, Harter and Sedlak 
(2004) and Kolodziej and Sedlak (2007) who found MDP in surface water in range of 0.4 – 1 
ng/l. The concentrations of NGL reported in this study (1.7-5.7 ng/l) corroborates the 
findings of Vulliet et al. (2008), who found that NGL in two samples from urban dam of 
water receiving effluents from various sewage treatment plants, as well as direct industrial 
                                                                                                                                                                       Chapter Nine 
 
138 
 
effluents in France were 5.3 and 7.0 ng/l.  Progesterone (PGT) concentrations in the 
Erewash River in the current study were lower with those of Kolpin et al. (2002) who found 
that PGT in the surface water was 199 ng/l, while in our results were below the limit of 
quantification (< 0.4 ng/l) in all samples along the river which is similar to Yoon et al. 
(2010) who reported < 0.5 ng/l and relatively consistent with Kuster et al (2008) (0.32-
1.39 ng/l). It is likely that Kolpin et al. (2002) are incorrect because others have reported 
lower values (Table 9.1). 
In terms of benzotriazoles concentration in the River Erewash, the findings of the current 
study do not support the previous research of Loos, Locoro and Contini (2010)  who found 
that BT was the higher than TT in Danube River in Europe. However, it should be noted that 
it is not easy to compare small streams and big rivers because of many factors that play an 
important role like river flow, dilution rate, and loading of organic pollution in terms of 
sewage treatment works existing on the river. The concentrations of BT in the 1st campaign 
in January were in the range of 118 – 1,270 ng/l which is in consistent with other work 
(Giger, Schaffner & Kohler, 2006; Kiss & Fries, 2009). While the 2nd campaign, BT 
concentrations were less than the 1st survey however, these results supports the findings of 
others (Loos et al., 2009; Loos, Locoro & Contini, 2010). Regarding to tolyltriazole, the 4 and 
5 isomers were not analyzed separately in this study; therefore the results are only 
compared with other studies which quantified the total tolyltriazole. The concentrations of 
TT along the River Erewash were quite similar in both campaigns ranging from 605 - 1855 
ng/l. Although these results are higher than some published studies (Weiss & Reemtsma, 
2005; Reemtsma et al., 2010), they are consistent with those of others (Weiss, Jakobs & 
Reemtsma, 2006; Jover, Matamoros & Bayona, 2009).  Although the concentrations of BT 
and TT at the mouth of the River Erewash were higher than at the mouth of the Danube 
River, the mass fluxes of benzotriazoles discharged from the River Erewash toward the 
River Trent are very low when compared to large rivers such as Danube. The mass 
discharged from the Danube River to the Black Sea is 33.8 tonnes of BT per year and 17.0 
t/year of TT (Loos, Locoro & Contini, 2010).  
One of the main objectives of modelling the rivers and consequently its catchment is to 
understand the behaviour of target compounds along the river. The importance of 
                                                                                                                                                                       Chapter Nine 
 
139 
 
modelling is to inform us about the zones or sections in the river that have a concentration 
higher than the allowable limits or which may exceed the limit of concern. Consequently it 
will be easier to decide how to control the pollution points, which is normally the effluents 
from STWs, and also tell us where to invest in order to improve the quality of the effluents 
and then the quality of the river water rather than random investment of the STW which 
might lead to an enhancement to the quality of effluent but not to the river water. 
The catchments of the Rivers Trent and Thames were modelled according to the principle 
of per capita load, due to the fact that the data about the concentrations of these chemicals 
from the discharging point (STWs and other points) were not available. The modelling of 
these two catchments showed that the highest concentrations for benzotriazoles were just 
downstream of the effluent discharges of the STWs existing on the streams and tributaries; 
this is not demonstrated in the main river (i.e. Trent and Thames). This is probably due to 
the flow rate in the main river compared to the other small rivers and also the dilution 
factor between the STW effluents to the receiving water body. Therefore it is worth 
investigating the load from specific STW that can contribute to the burden with high 
concentrations and flow rate in order to improve the overall quality by adding tertiary 
treatment instead of investing other STW that might not have a large impact at the 
catchment scale. 
In order to achieve the modelling, there are many criteria that should be considered and 
one of these important criteria is the degradation rate or the half life of the chemicals of 
interest. Therefore in this study the degradation test, for both group of chemicals 
(progestogens and benzotriazoles) was conducted, as the main mechanism of progestogens 
removal is degradation (Labadie & Budzinski, 2005a; Fan et al., 2011). 
The concentrations of progestogens were very low in samples taken for the degradation 
study, in agreement when progesterone was not detected Han River in South Korea and its 
tributaries (Yoon et al., 2010). In this study, and according to results, the degradation of 
progestogens was divided into three groups according to their half lives. The natural 
progestogen, progesterone (PGT), was degraded rapidly and the half life was less than one 
day. This is in accordance with Labadie and Budzinski (2005b) who found that the half-life 
                                                                                                                                                                       Chapter Nine 
 
140 
 
of progesterone was about 8 hours, although their samples were sewage effluent. However, 
in our study it was not planned to monitor the concentration of progesterone within the 
first day. Therefore it seems that the natural steroids are degraded quite rapidly in the 
aquatic environment, for example, both estrone and estriol, the natural estrogens, were 
found that losses had happened when they stored for a week (Baronti et al., 2000). The 
degradation of the synthetic progestogens was slower than that of the natural hormone 
under the same conditions and same findings were found by Chang et al. (2010).  
The other group of interest, benzotriazoles (BT and TT), were resistant to degradation 
during the test. This result is corroborated by others who have stated that benzotriazole 
was not biodegraded ( Hart et al., 2004; Weiss & Reemtsma, 2005; van Leerdam et al., 
2009), however some studies have stated that the 5 - TT isomer is more easy to biodegrade 
than 4 - TT isomer (Weiss & Reemtsma, 2005; Weiss, Jakobs & Reemtsma, 2006; Reemtsma 
et al., 2010). 
The results of this study indicate that there are some chemicals that may be of more 
concern because of their persistence. It was possible that high concentrations in water used 
for potable supply could result in their presence in tap waters. Benzotriazoles were the only 
chemicals studied and observed in the tap waters in this study and dishwasher detergents 
were identified as one possible source of these chemicals to the aquatic environment. 
Although the presence of chemicals in the environment and drinking water does not in itself 
pose a risk to health and the environment, there is concern that the possible effects of long 
term exposure to individual chemicals and / or mixtures of chemicals are not fully 
understood (Snyder et al., 2003; Jones, Lester & Voulvoulis, 2005). The implications of our 
findings depend to a large extent on the degree of (eco) toxicity of BT and TT. Chemicals are 
usually more toxic when administered chronically (long-term) than when exposure is acute 
(short-term). This difference can be expressed as the acute: chronic ratio. For many 
industrial chemicals, this ratio is 10 or less, meaning that the LOEC and NOEC derived from 
chronic toxicity tests are not appreciably lower than those derived from acute toxicity tests. 
However, if chemicals have specific modes of action (as, for example, pharmaceuticals do), 
then chronic toxicity tests often demonstrate that chemicals can be very much more toxic 
than anticipated based on the results of acute toxicity tests (Fent, 2008). For example, the 
                                                                                                                                                                       Chapter Nine 
 
141 
 
acute: chronic ratio of ethinyl estradiol is around 100,000 (Webb, 2004). This illustrates the 
importance of the current data gap with BT and TT; it is imperative to determine their 
chronic ecotoxicities (Harris et al., 2007) and data on carcinogenicity is conflicting (USEPA, 
2011). Although there seems to be no particular reason to think that BT and/or TT will 
have a high acute: chronic ratio, and hence be of more concern than appears to be the case 
based on acute ecotoxicity data, caution should be exercised for the following reason. Many 
azoles are very active chemicals, with specific modes of action: many (imidazoles and 
triazoles) are fungicides used in agriculture, and others (e.g. fadrazole) are used for anti-
estrogen treatment in diseases such as breast cancer (Trosken et al., 2004). Recent results 
have demonstrated that many commonly-used fungicides act as endocrine disrupters in 
vivo in both mammals (Taxvig et al., 2008) and fish (Rime et al., 2010). Structural alerts 
such as these can be useful in aiding the selection of appropriate chronic toxicity tests that 
should be helpful in determining whether or not BT and/or TT are significantly more toxic 
chronically than they are acutely. 
Adding further uncertainty to the toxicity of BT and TT is the possibility that BT is a human 
carcinogen. A Dutch committee concluded that the weight of evidence indicated that BT 
may be a possible genotoxic carcinogen, although it was highlighted that the database was 
inconclusive (DECOS, 2000). Based on that assessment, and structural analogy, Australian 
drinking water quality guidelines suggest a maximum permissible concentration of TT of 7 
ng/l (NRMMC-EPHC-NHMRC, 2008). Given this uncertainly, it could be strongly argued that 
the precautionary principle should be applied to both BT and TT, and exposure 
concentrations (to both aquatic wildlife and humans) minimised until appropriate chronic 
toxicity data become available on which to base any risk assessments.  
It is therefore apparent that although conventional treatment may be seen as effective (with 
> 90% removal), this may not be good enough. We can use modelling to inform us about 
where in the catchment we might most effectively invest in any further treatment processes 
required to reduce concentrations in effluents. Investment in tertiary treatment may also 
consider a number of factors, such as the effectiveness at different sites, presence of 
degradation products and costs, which may be important both financially and through 
energy use (UKWIR, 2002).   
 
 
 
 
 
 
 
 
 
 
 
 
 
Chapter Ten:  Conclusions  
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                         Chapter Ten 
 
143 
 
 
The overall aim of this research was to study the effectiveness of conventional and 
advanced wastewater treatment in reducing discharges of emerging contaminants. This aim 
was achieved by studying the fate of progestogens (one natural and nine synthetic) and 
benzotriazoles (BT and TT) via determining the occurrence and removal of progestogens 
and benzotriazoles in wastewaters and in the aquatic environment in the UK.  
  
The conclusions obtained throughout this research are: 
 
 
1. Progestogens and benzotriazoles were present in the sewage system. In terms of 
predominance, the natural hormone, progesterone, was the most predominant 
progestogens. However, the concentrations of benzotriazoles were two magnitudes 
higher than progestogens and tolyltriazole predominated at both STWs. 
 
2. Both the ASP and TF plant partially removed the compounds, and at both sites the 
sand filters contributed to improving overall removal. 
 
3. In advanced treatment at Hallam Fields STW, results show that three techniques 
(O3, GAC, and ClO2) were not able to remove progestogens significantly. However, 
this may be due to the low initial concentration of these chemicals and probably 
due to low O3 dose in terms of ozonation. However, a large reduction (73% - 90% 
for BT and 79% - 98% for TT) as observed for the benzotriazoles.  
 
4. The adsorption method represented by GAC seemed more effective than the other 
two advanced (oxidation) treatments, O3 and ClO2, hence the removal efficiency 
ranged from 60 – 98 % for both group of compounds. However, the O3 dose and 
contact time were low in this study and a range of factors would influence selection 
of tertiary processes.  
 
                                                                                                                                                                         Chapter Ten 
 
144 
 
5. In terms of degradation of progestogens in the river waters, the natural hormone 
was degraded rapidly (half-life < 24 hrs). Some synthetic progestogens had half-
lives of between 2 to 4 days, and others were more recalcitrant and their half-lives 
were more than 4 days. While the other group of chemicals, benzotriazoles, were 
not degraded during the 14 days of the experiment. 
 
6. Progestogens and benzotriazoles were present in the river waters. Concentrations 
of individual progestogens in the river water were relatively low, however the 
concentration of the sum of progestogens in the River Erewash was from 10.9 to 
27.0 ng/l. For benzotriazoles, the concentrations of BT and TT were two 
magnitudes higher than the progestogens and the general trend along the river 
showed an increase in their concentration. 
 
7. Two river catchments were modelled which indicated widespread occurrence of 
BT and TT, including in the waters used for abstraction for potable use. 
 
8. In terms of tap water, benzotriazoles were quantified in all tap water samples 
around Uxbridge – London. Benzotriazole was present at concentration higher than 
TT in all samples measured. The mean concentrations of BT and TT were 30.9 ng/l 
to 15.1 ng/l respectively.  
 
9. From the evaluation of possible inputs from dishwasher tablets and powders. It 
seems likely that they contribute significantly to concentrations of BT and TT 
present in the environment. Source control may be an effective way to improve the 
environmental quality. 
 
 
 
 
 
 
 
 
 
 
 
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Appendix 1:  Conventional Treatment 
 
 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
173 
 
Concentrations of progestogens in the settled sewage in ng/l at Hallam Fields sewage 
treatment work. 
 
Hallam 
Fields 
STW 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 18.1 20.1 64.5 26.7 13.7 5.7 9.0 27.2 26.3 36.4 
AM 12.5 < 2 4.2 < 0.4 < 0.8 3.6 < 2 13.5 15.7 35.3 
AM 10.5 < 2 29.5 < 0.4 < 0.8 < 0.8 < 2 15.8 40.9 36.7 
AM 24.0 < 2 24.6 < 0.4 < 0.8 12.5 < 2 34.1 36.1 55.1 
PM 23.1 13.8 < 3.2 19.8 15.2 8.6 5.8 24.6 32.9 38.2 
PM 25.1 < 2 96.5 < 0.4 < 0.8 < 0.8 29.5 18.5 44.0 < 3.2 
PM < 0.4 < 2 62.6 < 0.4 < 0.8 1.5 < 2 31.4 65.2 < 3.2 
PM 31.5 < 2 < 3.2 < 0.4 < 0.8 15.5 13.1 18.9 113.7 56.5 
 
 
 
 
 
Concentrations of progestogens in the settled sewage in ng/l at Newthorpe sewage 
treatment work. 
 
Newthorpe 
STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 9.0 7.3 < 3.2 27.7 10.3 12.9 4.2 16.1 25.2 29.1 
AM 19.9 < 2 71.4 6.2 < 0.8 16.3 < 2 6.3 37.3 < 3.2 
AM 16.0 < 2 40.8 27.3 < 0.8 18.4 < 2 < 4 44.0 < 3.2 
AM 9.2 17.5 27.6 34.3 28.7 20.4 < 2 < 4 60.0 33.1 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
174 
 
Concentrations of progestogens as a RGF feed in ng/l at Hallam Fields sewage 
treatment work. 
 
Hallam 
Fields 
STW 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 0.3 < 1 < 1.6 < 0.4 5.0 < 0.2 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 6.3 
AM 1.9 13.3 27.9 9.4 3.9 5.2 4.7 17.8 7.4 2.3 
AM 0.3 14.0 11.0 11.7 9.7 6.0 3.5 23.0 8.3 13.8 
PM 0.7 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 3.8 
PM 5.0 8.8 56.6 5.1 7.1 5.8 < 1 12.9 5.2 15.4 
PM 4.3 < 1 4.4 < 0.4 9.7 < 0.4 < 1 2.1 < 0.4 < 1.6 
PM < 0.2 13.6 < 0.8 5.7 4.8 < 0.4 < 1 5.9 8.7 < 1.6 
 
 
 
 
 
Concentrations of progestogens as a RGF feed in ng/l at Newthorpe sewage treatment 
work. 
 
Newthorpe 
STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 1.1 3.1 1.7 2.2 3.8 2.6 1.1 5.6 2.0 3.6 
AM 9.4 25.1 60.3 14.3 22.2 10.6 5.2 26.0 12.5 30.9 
AM 0.9 < 1 41.7 < 0.4 < 0.4 < 0.4 < 1 < 2 1.3 < 1.6 
AM < 0.2 < 1 21.0 < 0.4 4.7 < 0.2 < 1 < 2 < 0.4 16.1 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
175 
 
Concentrations of progestogens as a final effluent in ng/l at Hallam Fields sewage 
treatment work. 
 
Hallam 
Fields STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 5.8 9.6 5.2 8.8 5.5 8.0 1.1 8.3 7.2 < 1.6 
AM 0.3 < 1 19.2 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 5.8 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM 1.1 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 24.9 < 0.4 39.3 
PM 1.2 7.7 20.1 4.9 3.1 3.6 1.4 9.2 5.6 11.7 
PM 2.8 < 1 3.5 < 0.4 15.7 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM < 0.2 < 1 < 1.6 < 0.4 4.1 < 0.4 < 1 < 2 < 0.4 < 1.6 
 
 
 
 
 
Concentrations of progestogens as a final effluent in ng/l at Newthorpe sewage 
treatment work. 
 
Newthorpe 
STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM < 0.2 < 1 < 0.8 < 0.4 < 0.4 0.6 < 1 < 2 < 0.4 < 1.6 
AM 3.8 < 1 4.2 < 0.4 < 0.4 0.7 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 5.4 < 0.4 < 0.4 < 0.2 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 6.6 3.1 2.8 8.2 4.9 < 1 < 2 5.2 11.3 
 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
176 
 
Concentrations of benzotriazoles in the settled sewage in ng/l at Hallam Fields 
sewage treatment work. 
 
Hallam Fields STW BT TT 
AM 1050 1435 
AM 1400 4420 
AM 2545 1870 
AM No Peak No Peak 
PM 3330 3530 
PM 3115 3895 
PM 2595 3365 
PM 3340 4380 
 
 
 
 
 
Concentrations of benzotriazoles in the settled sewage in ng/l at Newthorpe sewage 
treatment work. 
 
Newthorpe  STW BT TT 
AM 1705 1840 
AM 1860 2210 
AM 3220 4490 
AM 2620 3400 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
177 
 
Concentrations of benzotriazoles as a RGF feed in ng/l at Hallam Fields sewage 
treatment work. 
 
Hallam Fields STW BT TT 
AM 800 1150 
AM 2345 2240 
AM 545 780 
AM 2790 3315 
PM 1310 1725 
PM 2490 2720 
PM 1655 2230 
PM 2290 2745 
 
 
 
 
 
Concentrations of benzotriazoles as a RGF feed in ng/l at Newthorpe sewage 
treatment work. 
 
Newthorpe  STW BT TT 
AM 560 745 
AM 1150 1895 
AM 1890 3030 
AM 2150 2830 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 1 
 
178 
 
Concentrations of benzotriazoles as a final effluent in ng/l at Hallam Fields sewage 
treatment work. 
 
Hallam Fields STW BT TT 
AM 670 855 
AM 2395 1985 
AM 745 1005 
AM 2100 2070 
PM 1425 1615 
PM NO IS NO IS 
PM 1175 1345 
PM 2150 2095 
 
 
 
 
 
Concentrations of benzotriazoles as a final effluent in ng/l at Newthorpe sewage 
treatment work. 
 
Newthorpe  STW BT TT 
AM 469 695 
AM 1035 1605 
AM 320 511 
AM 418 507 
 
 
 
 
 
 
 
 
 
 
 
 
 
Appendix 2:  Advanced Treatments 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 2 
 
180 
 
Concentrations of progestogens as a final effluent (pre-   ) in ng/l. 
 
Hallam 
Fields STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 5.8 9.6 5.2 8.8 5.5 8.0 1.1 8.3 7.2 < 1.6 
AM 0.3 < 1 19.2 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 5.8 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM 1.1 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 24.9 < 0.4 39.3 
PM 1.2 7.7 20.1 4.9 3.1 3.6 1.4 9.2 5.6 11.7 
PM 2.8 < 1 3.5 < 0.4 15.7 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM < 0.2 < 1 < 1.6 < 0.4 4.1 < 0.4 < 1 < 2 < 0.4 < 1.6 
 
 
 
Concentrations of progestogens after O3 treatment in ng/l. 
Hallam 
Field STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 2.1 < 1 < 1.6 < 0.4 0.5 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 2.6 < 1 < 1.6 < 0.4 2.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 1.1 5.6 3.0 3.5 5.5 2.7 1.1 4.9 4.0 4.4 
AM < 0.2 < 1 4.2 2.7 4.9 4.5 < 1 < 2 3.7 < 1.6 
PM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM 1.3 < 1 6.5 < 0.4 < 0.4 < 0.4 < 1 25.7 < 0.4 22.6 
PM 2.0 13.6 4.1 4.9 10.2 5.2 2.1 6.9 6.5 10.2 
PM 2.7 6.1 3.8 3.6 2.5 2.8 1.3 < 2 3.8 < 1.6 
 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 2 
 
181 
 
Concentrations of progestogens after GAC treatment in ng/l. 
Hallam 
Field 
STW 
CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 1.1 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM < 0.2 < 1 1.3 < 0.4 < 0.4 < 0.4 < 1 21.5 < 0.4 31.2 
PM < 0.2 9.9 7.6 9.9 6.4 3.0 1.7 6.9 5.6 12.1 
PM < 0.2 < 1 < 1.6 < 0.2 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM < 0.2 2.7 3.3 2.0 3.0 2.5 < 1 < 2 1.4 < 1.6 
 
Concentrations of progestogens after ClO2 treatment in ng/l. 
Hallam 
Field STW CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
AM 1.4 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 0.4 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 0.4 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
AM 1.8 7.4 4.1 3.3 3.1 4.1 < 1 6.0 6.2 4.2 
PM < 0.2 < 1 < 1.6 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM 1.7 5.1 3.1 4.6 5.1 4.3 1.5 4.3 3.7 < 1.6 
PM 1.8 < 1 1.7 < 0.4 < 0.4 < 0.4 < 1 < 2 < 0.4 < 1.6 
PM 3.9 4.1 1.8 2.0 2.1 2.9 1.7 < 2 2.0 < 1.6 
 
Concentrations of benzotriazoles in the final effluent (pre-   ) and after the three 
technologies in ng/l. 
  BT TT 
Final Effluent AM 625 2585 PM 410 1920 
Ozone (O3) AM 109 424 PM 163 510 
Granular Activated Carbon (GAC) AM 47 59 PM 53 42 
Chlorine dioxide (ClO2) AM 133 410 PM 148 528 
 
 
 
 
 
 
 
 
Appendix 3:  Degradation Test 
 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 3 
 
183 
 
 
Main measured parameters throughout the test (n=15). 
 PH Dissolved Oxygen mg/l Temperature C 
DAY Tank 1 Tank 2 Tank 1 Tank 2 Tank 1 Tank 2 
0 8.69 8.69 7.33 7.8 20.7 20.4 
1 8.58 8.63 7.61 7.93 21 20.4 
2 8.69 8.69 7.53 7.64 22.3 20.8 
3 8.58 8.58 7.69 7.78 21.5 19.3 
4 8.59 8.56 7.92 8 19.6 19.3 
5 8.68 8.57 8.24 8.2 21.5 21 
6 8.61 8.65 8.12 8.1 22.8 22.1 
7 8.59 8.6 8.2 8.28 21.1 21 
8 8.59 8.6 8.35 8.46 20.8 19.6 
9 8.6 8.61 8.31 8.21 21.3 20.8 
10 8.66 8.67 7.84 8.2 25.5 23.8 
11 8.64 8.67 7.8 8 25 23.6 
12 8.58 8.66 7.8 7.8 25 24.7 
13 8.66 8.67 7.9 7.7 24.7 24.9 
14 6.67 6.6 8.7 8.23 24.3 24.7 
 
Concentration of benzotriazoles throughout the 14 day test. 
 BT TT 
Day Tank 1 Tank 2 Tank 1 Tank 2 
0 655 650 2,370 2,365 
1 695 670 2,425 2,430 
2 640 665 2,410 2,350 
3 670 635 2,420 2,440 
4 655 650 2,430 2,440 
5 650 670 2,485 2,495 
6 625 660 2,440 2,485 
7 650 625 2,450 2,415 
8 680 615 2,405 2,370 
9 665 670 2,465 2,420 
10 660 645 2,470 2,465 
11 655 670 2,415 2,440 
12 685 680 2,430 2,505 
13 690 680 2,500 2,465 
14 685 685 2,505 2,460 
                                                                                                                                                                                                                                                     Appendix 3 
 
184 
 
 
Concentration of progestogens throughout the 14 day test. 
 
 
 CPA DSP DHG MDP MPA MTA NTD NGL PGT TBL 
DAY Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
Tank 
1 
Tank 
2 
0 538 509 663 645 532 499 646 623 548 540 568 551 507 495 532 483 401 420 662 627 
1 481 429 579 534 295 276 152 175 488 460 494 448 448 401 491 465 6 6 623 603 
2 392 371 476 458 148 174 42 50 411 385 422 392 388 381 432 421 5 2 540 585 
3 333 363 359 301 132 150 19 17 333 302 314 298 334 359 424 369 < 0.4 < 0.4 515 462 
4 304 286 300 262 101 123 6 18 294 296 295 282 318 315 349 346 2 5 423 413 
5 296 282 237 236 94 88 9 7 276 273 264 234 255 238 332 290 < 0.4 < 0.4 381 358 
6 251 265 182 218 55 69 4 3 228 251 209 214 218 181 224 265 < 0.4 < 0.4 239 276 
7 226 195 182 170 50 47 10 5 198 184 190 154 171 132 171 132 8 < 0.4 219 173 
8 197 165 118 119 38 35 4 < 0.4 167 146 156 147 138 113 154 141 < 0.4 < 0.4 210 167 
9 206 169 118 119 13 15 2 2 152 133 151 116 109 95 148 126 < 0.4 < 0.4 153 138 
10 195 169 117 113 7 5 < 0.4 < 0.4 132 103 119 112 97 66 133 104 < 0.4 < 0.4 151 111 
11 193 161 102 107 9 <0.8 < 0.4 < 0.4 117 94 98 75 47 38 88 74 < 0.4 < 0.4 89 101 
12 130 118 91 77 3 4 < 0.4 < 0.4 75 61 61 51 28 32 46 58 < 0.4 < 0.4 47 50 
13 110 96 72 75 3 4 9 1 64 59 58 46 19 17 39 36 8 < 0.4 34 40 
14 90 80 49 53 4 5 4 < 0.4 62 54 38 28 6 8 19 19 3 2 13 25 
                                                                                                                                                                           Appendix 3 
 
185 
 
 
 
Concentration of medroxyprogesterone throughout the 14 day test 
 
 
Concentration of dydrogesterone throughout the 14 day test. 
 
 
 
 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
MD
P   
ng/
l 
Time (day) 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
DH
G   
ng/
l 
Time (day) 
                                                                                                                                                                           Appendix 3 
 
186 
 
 
 
Concentration of norethindrone throughout the 14 day test. 
 
 
 
Concentration of tibolone throughout the 14 day test. 
 
 
 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
NTD
    ng
/l 
Time (day) 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
TB
L   
 ng
/l 
Time (day) 
                                                                                                                                                                           Appendix 3 
 
187 
 
 
 
Concentration of megestrel-acetate throughout the 14 day test. 
 
 
 
Concentration of medroxyprogesterone- acetate throughout the 14 day test. 
 
 
 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
MT
A   
 ng/
l 
Time (day) 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
MP
A   
 ng
/l 
Time (day) 
                                                                                                                                                                           Appendix 3 
 
188 
 
 
 
Concentration of drosprinone throughout the 14 day test. 
 
 
0 
100 
200 
300 
400 
500 
600 
700 
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 
DSP
    n
g/
l 
Time (day) 
 
 
 
 
 
 
 
 
 
 
 
 
Appendix 4:  Modelling 
 
 
 
 
 
 
 
 
 
 
 
 
 
                                                                                                                                                                           Appendix 4 
 
190 
 
 Fluxes of BT and TT in g/day discharged each day from STW to the River Erewash 
(6th January 2009). 
STW  BT(ng/l) TT (ng/l) Q m3/d  BT  g/day  TT g/day 
Kirkby  FE (N/ASP) 840 2,685 5,970 5.0 16.0 
Pinxton FE (N/ASP) 1,335 4,125 4,242 5.7 17.5 
Pye Bridge FE (TF) 2,895 5,450 2,048 5.9 11.2 
Milnhay FE (N/ASP) 1,655 3,400 7,050 11.7 24.0 
Newthorpe FE (TF) 2,470 5,500 10,282 25.4 56.5 
Hallam Fields FE (N/ASP) 2,090 5,700 10,022 20.9 57.1 
Stapleford FE (N/ASP) 1,375 3,665 5,737 7.9 21.0 
Toton FE (N/ASP) 3,605 5,200 16,762 60.4 87.2 
 
 
Concentrations of BT and TT in ng/l along the River Erewash (6th January 2009). 
Sampling point BT (ng/l) TT (ng/l) 
U/S of Kirkby STW 81 68 
D/S Kirkby STW  182 605 
D/S Pinxton STW  985 995 
D/S Pye Bridge STW  1,270 1,380 
U/S of Milnhay STW 1,020 1,335 
D/S of Milnhay STW 740 1,105 
D/S of Gilt brook confluence 965 1,795 
U/S of Hallam Fields STW 930 1,855 
D/S of Hallam Fields STW & Nut brook  735 1,520 
D/S Stapleford STW  895 1,745 
D/S of Toton STW  1,050 1,820 
 
Concentrations of BT and TT in ng/l from brooks as tributary to the River Erewash 
(6th January 2009). 
Sample Name BT (ng/l) TT (ng/l) 
Bagthorpe brook 23 35 
Nethergreen brook 13 33 
Gilt brook U/S of Newthorpe STW 118 20 
Nut brook 21 38 
 
                                                                                                                                                                           Appendix 4 
 
191 
 
Fluxes of BT and TT in g/day discharged each day from STW to the River Erewash 
(29th October 2009). 
STW  BT(ng/l) TT(ng/l) Q m3/d  BT  g/day  TT g/day 
Kirkby  FE (N/ASP) 497 2,310 5,970 3.0 13.8 
Pinxton FE (N/ASP) 714 2,120 4,242 3.0 9.0 
Pye Bridge FE (TF) 646 2,380 2,048 1.3 4.9 
Milnhay FE (N/ASP) 496 2,730 7,050 3.5 19.2 
Newthorpe FE (TF) 749 2,320 10,282 7.7 23.9 
Hallam Fields FE (N/ASP) 867 2,040 1,0022 8.7 20.4 
Stapleford FE (N/ASP) 666 2,450 5,737 3.8 14.1 
Toton FE (N/ASP) 581 2,070 16,762 9.7 34.7 
 
 
Concentrations of BT and TT in ng/l along the River Erewash (29th October 2009). 
Sampling point BT (ng/l) TT (ng/l) 
U/S of Kirkby STW 50.8 84.3 
D/S Kirkby STW  224 700 
D/S Pinxton STW  397 1,080 
D/S Pye Bridge STW  431 1,280 
U/S of Milnhay STW 426 1,010 
D/S of Milnhay STW 382 1,110 
D/S of Gilt brook confluence 407 1,570 
U/S of Hallam Fields STW 449 1,400 
D/S of Hallam Fields STW & Nut brook  338 1,090 
D/S Stapleford STW  410 1,420 
D/S of Toton STW  434 1,530 
 
Concentrations of BT and TT in ng/l from brooks as tributary to the River Erewash 
(29th October 2009). 
Sample Name BT (ng/l) TT (ng/l) 
Bagthorpe brook 31 35 
Nethergreen brook 10 18 
Gilt brook U/S of Newthorpe STW 97 64 
Nut brook 16 29 
 
 
 
 
 
 
 
 
 
Appendix 5:  Drinking Water and Detergents 
 
 
 
 
 
 
 
 
                                                                                                                                                                                                                                                     Appendix 5 
 
193 
 
Concentrations of BT and TT in ng/l from 80 tap water samples around Uxbridge. 
 
 
Sample Name BT TT Sample Name BT TT Sample Name BT TT Sample Name BT TT 
Sample_1 50.2 12.8 Sample_21 48.8 15.8 Sample_41 36.8 14.1 Sample_61 46 12.2 
Sample_2 51.8 12.6 Sample_22 27.6 10.7 Sample_42 35.6 12.5 Sample_62 47 14 
Sample_3 18.5 4.2 Sample_23 21.4 4.4 Sample_43 15.3 5.6 Sample_63 13.6 4.4 
Sample_4 26.4 18.9 Sample_24 18.9 20.2 Sample_44 16.6 17.6 Sample_64 17.7 18.7 
Sample_5 34.6 14.5 Sample_25 13.5 10.2 Sample_45 29.4 11.2 Sample_65 39.8 13.5 
Sample_6 28.6 19.7 Sample_26 24.4 34.4 Sample_46 30 37.4 Sample_66 17.8 20.2 
Sample_7 58.2 15.5 Sample_27 44.4 12.8 Sample_47 32.4 10.5 Sample_67 42.4 15.4 
Sample_8 44.6 10.5 Sample_28 49.4 15.7 Sample_48 37.8 12.7 Sample_68 42.7 22.8 
Sample_9 1.7 0.8 Sample_29 0.7 0.7 Sample_49 12.6 1.4 Sample_69 17.7 1.7 
Sample_10 45.2 13.1 Sample_30 54 15.5 Sample_50 35.8 12.1 Sample_70 32.6 17.1 
Sample_11 47.4 9.5 Sample_31 48 10.5 Sample_51 35.8 10.4 Sample_71 44 14.6 
Sample_12 62.8 49.8 Sample_32 79.4 69.8 Sample_52 66.8 66 Sample_72 67.6 67.4 
Sample_13 63.5 44.9 Sample_33 62.4 47.6 Sample_53 42.4 45.4 Sample_73 54 47.6 
Sample_14 33 11.5 Sample_34 26.2 12.8 Sample_54 30.6 10.9 Sample_74 45.6 10.5 
Sample_15 5.3 0.8 Sample_35 0.6 0.5 Sample_55 0.8 0.4 Sample_75 1.9 0.6 
Sample_16 17.7 3.4 Sample_36 20.4 7.3 Sample_56 28 15.5 Sample_76 17.5 10 
Sample_17 6.3 0.8 Sample_37 0.8 0.5 Sample_57 1.1 0.5 Sample_77 3.3 0.5 
Sample_18 49.4 11.8 Sample_38 29.2 11.8 Sample_58 31.6 10.7 Sample_78 43.6 14.9 
Sample_19 21.2 14.4 Sample_39 22.5 7.1 Sample_59 22.3 11.5 Sample_79 42.4 10.1 
Sample_20 17.1 2 Sample_40 5 1.5 Sample_60 9.6 4.4 Sample_80 3.9 2.2 
                                                                                                                                                                           Appendix 5 
 
194 
 
 
Concentrations of BT and TT in ng/l of dishwasher detergents from UK markets. 
 
  mg per 20g mg per 20g   
  Batch (1) Batch (2)   
Sample Name  Type BT TT BT TT Average BT Average TT 
Finish tablet  57.3  61.7  60 
Finish powder  12.0  21.9  17 
fairy tablet 5.0  4.0  4.5  
Sainsbury's tablet 1.0  0.8  0.9  
Sainsbury's powder 17.8  15.0  16.4  
Morrison tablet 0.6  0.5  0.5  
Morrison powder 21.2  12.6  16.9  
ASDA tablet 1.3  ---  1.3  
ASDA powder 2.5  2.1  2.3  
TESCO tablet 2.9  1.5  2.2