oliver grievson thesis

i

OLIVER JAMES GRIEVSON

THE REMOVAL OF PERMETHRIN AND TRIBUTYLTIN FROM WASTEWATER USING

ADVANCED OXIDATION PROCESS AND ADSORPTION

SCHOOL OF APPLIED SCIENCE

MSc WATER & WASTEWATER TECHNOLOGY

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SCHOOL OF APPLIED SCIENCE

MSc WATER & WASTEWATER TECHNOLOGY

2007

OLIVER JAMES GRIEVSON

THE REMOVAL OF PERMETHRIN AND TRIBUTYLTIN FROM

WASTEWATER USING ADVANCED OXIDATION PROCESS AND ADSORPTION

SUPERVISOR: PROFESSOR SIMON PARSONS

5th September 2007

This thesis is submitted in partial (40%) weighting fulfilment of the requirements for the degree of MSc Water and Wastewater Technology

© Cranfield University 2007

No part of this publication may be reproduced without the written permission of the

copyright holder.

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Abstract

Permethrin and tributyltin (TBT) are a persistent problem in the aquatic

environment with annual environmental quality standard failures reported in the

waterways and coastal waters of the United Kingdom. Their presence has been

reported in wastewater treatment plant effluents, methods of their removal are

required.

This paper examines the degradation of permethrin and TBT with three

advanced oxidation processes; UV-photolysis, UV/H2O2 and Fenton’s reagent.

The effectiveness and cost of each of the three processes is compared to

adsorption onto granular activated carbon (GAC).

UV/H2O2 was able to reduce permethrin and TBT simultaneously in water with

permethrin being removed to below the limit of detection and TBT removed to

89% of its initial concentration. UV-photolysis was able to remove both

permethrin in spiked deionised water but wasn’t as effective for TBT removal.

Fenton’s reagent wasn’t as effective as either of the photolysis methods for the

removal of the target compounds and adsorption, experimentally, wasn’t as

effective as it should have been. This will be expanded upon in the results

section.

The final conclusion, is that the cost of treatment was significant and for the

AOP’s predictions were £8.14 - £28.95 per m3, in comparison to treatment by

adsorption to GAC ranging between £0.02 – £0.07 per m3.

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Executive Summary

Introduction

The introduction to this project introduces the issues of permethrin and TBT as

toxic micro-pollutants, that they are ubiquitous within the aquatic environment in

the United Kingdom and the failures of environmental quality standards,

particularly TBT. The levels present in UK wastewater treatment plants are then

addressed and the applicability of advanced oxidation processes to their

removal from wastewater.

Literature review

The literature review looks at the chemical behaviour, toxicity and

environmental fate of both permethrin and TBT and looks at levels found within

the aquatic environment, in particular levels within wastewater treatment plants.

Advanced oxidation processes (AOP’s) are then addressed with the

mechanisms of how they work and then case studies of their use in the

degradation of organic compounds, with particular reference to permethrin and

TBT.

Methods and Materials

The method and materials section of this report details the degradation

experiments undertaken and gives details of the ethylation and novel analytical

procedure for the simultaneous analysis of permethrin and TBT by gas

chromatography-mass spectrophotometry.

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Results and discussion

The results and discussion section firstly reviews the method development used

for the determination of permethrin and TBT. Then it goes onto look at the

results of the degradation experiments in deionised and wastewater.

The discussion goes on to look at the mechanisms of the degradation of

permethrin, TBT and other compounds that are degraded by similar

mechanisms. The photolability of permethrin and the lack of photolability of TBT

is discussed. The degradation of TBT using the hydroxyl radical produced by

UV/H2O2, Fenton’s reagent and coincidentally by UV/Fe(III) is discussed.

Finally the costs of treating permethrin and TBT by AOP’s are looked at and

compared to the cost of treatment by adsorption.

Conclusion

The main conclusions that this study comes to is that amongst the AOP’s used

UV/H2O2 is the most effective technique for the simultaneous degradation of

permethrin and TBT but that its is an economically unfeasible technique when

compared to adsorption onto GAC. It also concludes that further work is needed

into the degradation products formed and whether different AOP’s maybe more

effective and cheaper to use. Another area of further study is in to whether other

types of adsorbents maybe more effective at removing the target compounds

and how applicable this work is to un-spiked samples in treatment plant scale

tertiary wastewaters.

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Table of Contents

1.0 Introduction ........................................................................... 1

2.0 Literature review ................................................................... 4

2.1 Target compounds............................................................................. 4

2.1.1 Permethrin.................................................................................... 4

2.1.2 Tributyktin..................................................................................... 8

2.2 Advanced Oxidation Processes & Adsorption .............................. 12

2.2.1 UV-Photolysis............................................................................. 13

2.2.2 UV-Photolysis & hydrogen peroxide (UV/H2O2) ......................... 16

2.2.3 Fenton’s reagent (Ferrous sulphate & hydrogen peroxide) ........ 19

2.2.4 Adsorption.................................................................................. 22

2.3 Current study.................................................................................... 24

3.0 Objectives............................................................................ 26

4.0 Paper for publication .......................................................... 27

4.1 Introduction ............................................................................. 29

4.2 Materials & Methods ................................................................. 32

4.2.1 Reagents......................................................................................... 32

4.2.2 Samples .......................................................................................... 33

4.2.3 Degradation experiments ................................................................ 33

4.2.3.1 Conditions for UV degradation experiments............................ 33

4.2.3.2 Spiked deionised water degradation experiments................... 34

4.2.3.3 Spiked wastewater degradation experiments.......................... 34

4.2.4 Ethylation/Extraction........................................................................ 35

4.2.5 Instrumental .................................................................................... 35

4.3. Results................................................................................... 37

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4.3.1 Method development....................................................................... 37

4.3.2 Control degradation experiments .................................................... 38

4.3.3 Direct & indirect photolysis .............................................................. 39

4.3.4 Fenton’s reagent degradation experiments ..................................... 41

4.3.5 Adsorption experiments................................................................... 42

4.3.6 Rate constants, quantum yields & energy consumption................. 42

4.4. Discussion.............................................................................. 44

4.4.1 Mechanisms of degradation ............................................................ 44

4.4.2 Costs of treatment ........................................................................... 47

4.5. Conclusion ............................................................................. 48

4.6 Acknowledgements .................................................................. 49

4.7. References ............................................................................. 50

4.8 Tables ..................................................................................... 55

4.9 Figures.................................................................................... 60

5.0 References........................................................................... 65

Appendix A : Methodology....................................................... 71

A 1.1 Performance characteristics of the method .............................. 72

A 1.2 Principle ........................................................................................ 73

A 1.3 Reagents ....................................................................................... 74

A 1.4 Apparatus...................................................................................... 76

A 1.5 Procedure...................................................................................... 77

A 1.5.1 Degradation. ........................................................................... 77

A 1.5.2 Ethylation................................................................................ 82

A 1.5.3 Instrumental analysis .............................................................. 83

A 1.6 Calculation .................................................................................... 84

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Appendix B: Uridine Actinometry ............................................ 85

B 1.0 Aim ...................................................................................... 86

B 1.1 Methodology ................................................................................. 86

B 1.1.1 Principle .................................................................................. 86

B 1.1.2 Equipment............................................................................... 86

AP 2.1.3 Reagents .............................................................................. 87

B 1.1.4 Procedure ............................................................................... 88

B 1.1.5 Calculations ............................................................................ 89

B 1.2 Results........................................................................................... 90

B 1.3 Conclusions .................................................................................. 94

Appendix C: Raw data .............................................................. 95

Appendix D: Water Research Guide for authors .................. 103

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List of tables

Table 2.1: Acute toxicity of permethrin to fish species...........................................6

Table 2.2: Oxidation potential of common species...............................................13

Table 2.3: Experimental conditions of UV degradation case studies. ...............16

Table 2.4: Experimental conditions of UV/H2O2 degradation case studies. .....19

Table 2.5: Experimental conditions of Fenton’s reagent degradation case

studies. ..........................................................................................22

Table 2.6: Experimental conditions of adsorption case studies. ........................24

Table 4.1: Experimental conditions for spiked deionised degradation

experiments..............................................................................................55

Table 4.2: Experimental conditions for spiked wastewater degradation

experiments..............................................................................................55

Table 4.3: Table of quantum yield, rate constants & EEO values for spiked

deionised water experiments...........................................................56-57

Table 4.4: Table of quantum yield, rate constants & EEO values for spiked

wastewater experiments ........................................................................58

Table 4.5: Quantum yields, rate constants and EEO values of selected

compounds...............................................................................................59

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List of Figures

Figure 1.1 Pesticide environmental quality standard failures in 2005. ................1

Figure 2.1: Chemical structure & environmental behaviour of permethrin ..... …5

Figure 2.2: Chemical structure & environmental behaviour of tributyltin ........... 8

Figure 2.3: Mass fluxes of total organotin through a wastewater treatment plant

……………………………………………………………………………11

Figure 4.1: Example chromatogram from the GC-MS...........................................60

Figure 4.2: Permethrin and TBT reduction by UV and UV/H2O2 in spiked

deionised water ...........................................................……………61

Figure 4.3: Permethrin and TBT reduction by UV and UV/H2O2 in spiked

wastewater ...............................................................................................62

Figure 4.4: Permethrin & TBT reduction by Fenton’s reagent in deionised

water..........................................................................................................63

Figure 4.5: Permethrin and TBT reduction by adsorption onto Norit GAC 1240

in spiked wastewater. .............................................................................64

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Nomenclature

Φ quantum yield

amu atomic mass unit

AOP’s advanced oxidation processes

COD chemical oxygen demand

d20 density at 20ºC

EQS environmental quality standards

g/d grams per day

GAC granular activated carbon

GC-ECD gas chromatography electron capture detector

GC-FPD gas chromatography flame photometric detector

GC-MS gas chromatography mass spectrometer

hv photon’s energy

Koc organic carbon absorption coefficient

Kow octanol water partition coefficient

kWh kilowatt hour

LC50 lethal concentration causing the death of 50% of the population

LD50 lethal dose causing the death of 50% of the population

PAC powdered activated carbon

TBT tributyltin

TCE trichloroethylene

UV ultraviolet

UV/H2O2 ultraviolet photolysis/ hydrogen peroxide advanced oxidation

process

W m-2 watts per square metre

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Acknowledgements

I would like to thank my supervisor Professor Simon Parsons for all of his efforts

and help in this project, especially for all of his reading of draft after draft and for

all of his editing skills and feedback.

I would also like to acknowledge the support of United Utilities in the funding of

this project as part of the STAMP scheme.

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1.0 Introduction

Tributyltin (TBT) and permethrin can be classed as two of many micro-

pollutants present in UK waters that cause problems in the natural environment.

The toxicity of TBT has been well documented especially its properties as an

endocrine disruptor and its previous impacts on the oyster industry (Alzieu,

1991). Permethrin is as well documented and its effects on aquatic eco-systems

can include invertebrate and fish deaths (Kamrin, 1997).

The prevalence of both of these compounds meant that between 2003-2005

there were a total of 53 failures of environmental quality standards (EQS) in

freshwaters from TBT and 17 failures in freshwaters from a combination of

cyfluthrin and permethrin (Environment Agency, 2007). The following figure

shows that these failures in 2005 were distributed throughout the United

Kingdom.

Figure 1.1 Pesticide environmental quality standard failures in 2005 (Environment Agency, 2007).

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TBT has been legislated since 1982 as a result of damage to the oyster

industry, with a standard set at 20 ng L-1 (Alzieu, 1991) and later in the United

Kingdom in 1986 (Clark et al, 1998). Current proposed legislation as part of the

Water Framework directive in the proposed directive on environmental quality

standards in the field of water policy is to see the maximum allowable

concentration of TBT set to fall to 1.5 ng/L and an average annual concentration

of 0.2 ng L-1 (Commission of the European Communities, 2006).

Environmental quality standards for permethrin are set at a local level by the UK

Environment Agency and permethrin is classed as a dangerous substance

under the Dangerous Substance Regulations (Environment Agency, 2007).

Permethrin and TBT have been measured in wastewater treatment plants at

concentrations up to 81 µg L-1 for permethrin (Kupper et al, 2006) and 0.22

µg L-1 for TBT (Fent & Muller, 1991) their removal from the wastewater

treatment process is imperative in order to comply with the proposed UK and

EU legislation.

Whilst a number of major studies have reported that the major route of both

permethrin and TBT within the wastewater environment is to be adsorbed to the

solids and get captured with the sludge (Fent, 1996; Plagellat, 2004) however

this will not remove either compound in the liquid phase to below the European

limit of 1.5 ng L-1 (Schafran, 2003).

As a result of this, it is necessary to look at treatment methods for the removal

of both permethrin and TBT from wastewater. Due to both compounds high

affinity to be adsorbed, the use of granular activated carbon (GAC) is a

possibility and has been studied previously (Schafran, 2003) and found to be

effective but not enough to remove TBT to below the regulated concentration of

50 ng L-1, in the shipyard waters that were studied. Due to the GAC’s inability to

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reduce TBT to below the legislative limit Schafran also investigated the use of

UV/H2O2 advanced oxidation process and found it to be an effective process in

the removal of TBT from shipyard waters.

The aim of most advanced oxidation processes (AOP’s) is to produce the

hydroxyl radical in order to mineralise organic compounds to less toxic or ideally

harmless inorganic molecules (Parsons, 2004). In this study the advanced

oxidation process’s that are being used are UV photolysis in the UV-C

waveband at 254nm, a combination of UV photolysis and hydrogen peroxide

and finally Fenton’s reagent (a mixture of ferrous iron and hydrogen peroxide).

Their removal from tertiary wastewater streams either by degradation or by

adsorption onto GAC will be examined in terms of the effectiveness of the

techniques and their applicability to the wastewater industry.

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2.0 Literature review

This literature review will look at the two target compounds of this study,

permethrin and TBT, their uses, their environmental fate and their toxicity.

Finally, any relevant studies to their occurrence within wastewater treatment

plants and their environmental fate will be reviewed. The review will then look at

the four main removal methods that are going to be used in this study, UV-

photolysis, UV/Hydrogen peroxide, Fenton’s reagent and adsorption. The

mechanisms of the methods will be explained, and then studies of their use in

removing the target compounds reviewed.

2.1 Target compounds

In this study the two main compounds that are going to be reviewed are

permethrin and TBT.

2.1.1 Permethrin

Permethrin (or to use its chemical name: 3-phenoxybenzyl (1RS)-cis, trans -3-

(2,2-dichlorovinyl)–2,2-dimethylcyclpropanecarboxylate) is a synthetic

pyrethroid insecticide used in a wide variety of sheep dips (Cooke et al, 2004),

and on agricultural crops to control biting flies, cockroaches and ectoparasites

(Kamrin, 1997). Details of permethrin’s chemical structure and its behaviour in

the environment are contained in Figure 2.1.

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It is practically non-toxic to mammalian life with reported LD50 in rats through the

oral route of 430-4500 mg kg-1. In

humans, permethrin is rapidly

metabolised and excreted and does

not significantly persist in the human

body (Kamrin, 1997).Permethrin

does have a significant impact on

aquatic ecosystems as it destroys

both the quality and quantity of

insects and invertebrates with LC50

concentrations of less than 1 µg L-1

being fatal (Kamrin, 1997). It is also

highly toxic to most fish especially at

lower temperatures and especially for

smaller fish (Sánchez-Fortún &

Barahona, 2005). LC50

concentrations for aquatic organisms range from 0.075 µg L-1 for Daphnia

Magna to 9.8 µg L-1 for Rainbow trout (Imgrund, 2003). There are a variety of

toxicities of permethrin depending on the species of fish, some LC50 values are

in Table 2.1.

Figure 2.1: Permethrin

Chemical Formula: C21H20Cl2O3 CAS No: 52645-53-1 Molecular Weight: 391.288 Melting point (ºC): 34 Boiling point (ºC): 200 Density (g cm3) 1.23 Solubility in water (mg l-1) 0.2 KOC (mL g-1) 100,000 Kow (Log P) 6.5 (Lide, 2005) (Lee et al, 2002)

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Table 2.1: Acute toxicity of permethrin to fish species (Baser et al., 2003)

Species Duration of test (hrs) LC50 (µg L-1)

Salmo salar 96 12

Oryzias lapites 48 41

Micropterus salmoides 96 8.5

Salvelinus fautinalis 96 3.2

Leopomis macrochirus 96 5

Cyprinodon variegates 96 7.8

Stripped bass 96 16.1

Menidia beryllina 96 0.062

Paleomonetes pugio 48 0.049

Tilapia zillii 48 49

Due to its high KOC value (Figure 2.1) the environmental fate of permethrin is to

be tightly bound in the soil or within a wastewater environment to the sewage

sludge. This is especially the case when the soils or sludge contain a high

organic matter content (Kamrin, 1997). Due to its low solubility in water and its

affinity for organic carbon, once it is bound in the sludge it is not very mobile

and will be readily broken down by micro-organisms (Kamrin, 1997). Permethrin

has a reported average half-life in sludge of between 30 & 38 days (Kamrin

1997 & Imgrund 2003).

Plagellat (2004) reported removal of permethrin from the final effluent of

wastewater treatment plants at greater than 94%. This identified that removal by

adsorption to the sewage sludge within the wastewater treatment process was

very dependant on the type of treatment process used but the adsorption

ranged from 4-15% of the incoming load. The rest of the removal (i.e. 85-96% is

not explained. This study also identified that private households were a

significant source of permethrin and TBT.

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Kupper et al (2006) reported influent concentrations of permethrin into a

conventional activated sludge wastewater treatment process up to 81 µg L-1. In

Kupper’s study water was spiked up to 544 ng L-1, permethrin concentrations

after primary treatment were reduced by 20% and by the end of the wastewater

treatment process there had been a decrease in permethrin concentrations of

92% (to a concentration of 20 ng L-1). The main removal mechanisms that were

identified were the adsorption of permethrin onto the sewage sludge and

biodegradation. The removal of 20% in the primary treatment stage was in a

similar range to Plagellat (2004) who reported a 15% removal due to adsorption

onto the sewage sludge in the primary treatment stage (Plagellat, 2004).

Contrary to the figure of 15-20% removal in the primary treatment process

(Plagellat, 2004, Kupper et al, 2006) Kirk et al (1989) reported a removal of up

to 61% of permethrin in batch studies on the laboratory scale, but with an

incoming concentration of 50µg L-1. However once Kirk et al (1989) worked on

a larger scale with continuous flow activated sludge simulation the removal of

permethrin by adsorption was 10-30%. The study by Kirk et al (1989) also

looked at the degradation of permethrin during the sludge treatment processes

and found removal of permethrin from the sewage sludge over a 32 day

anaerobic digestion period could reach up to 96%.

Rogers et al (1989) study on the occurrence of permethrin in twelve UK sewage

sludges showed concentrations of permethrin up to 40.8 mg kg-1 (dry weight).

This shows “that permethrin is sorbed onto sludge solids during sewage

treatment” (Rogers et al. 1989).

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2.1.2 Tributyltin

TBT is a sub-group of the trialkyl organotin compounds (Etoxnet, 2007). TBT

was first used in 1959 as an anti-fouling additive in marine paints (Clark et al,

1988) until the practise was

stopped in January 2003 (Song et

al., 2005). TBT is also used in wood

treatment and preservation, as an

anti-fungicide in the textile industry,

in wood pulp and paper mill

systems, in breweries (Etoxnet,

2007), and as stabilizing additives

in poly-vinyl chloride and other

polymers (Hoch & Schweisig, 2004)

Details on TBT’s chemical structure

and behaviour in the environment

are contained in Figure 2.2.

TBT is moderately toxic via oral

ingestion and through the skin. Oral

LD50 values range between 55-87

mg kg-1 in mice & rats. In humans a strong irritating effect has been recorded

and if concentrations are high enough, irritated skin, dizziness and flu-like

symptoms (Etoxnet, 2007).

Where TBT is particularly toxic is in the aquatic environment. It has been known

to cause defective shell growth in oyster populations, and cause the

development of male genitalia in the female dog whelk, and cause

immunosupression in fish populations (Yebra et al, 2004). This was extensively

studied in two papers by Alzieu (1991 & 1998) where problems with oyster

growth, specifically Crassostrea gigas in the Bay of Archaron, prompted the first

Figure 2.2: TBT

Sn

H Chemical Formula: C12H28Sn CAS No: 688-73-3 Molecular Weight: 291.060 Melting point (ºC): 76 Boiling point (ºC): 113 Density (g cm3): 1.103 Solubility in water (mg l-1): 4 KOC (mL g-1): 1600 Kow (Log P): 4.1 (Lide, 2005) (Weidenhaupt, 1997)

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regulations on TBT in the aquatic environment. In 1982 the French government

initially passed legislation banning the use of TBTs on all boats under 25

tonnes. This was then extended to cover all boats under 25m length and fishing

apparatus.

In Alzieu’s study in 1998 it confirmed that the actions of the French government

had resulted in a decrease in TBT concentrations. In 1986 the UK government

instigated a safe water concentration of 20ng L-1 (Clark et al., 1988). In 1987 the

state of Virginia in the United States imposed a limit of 50 ng L-1 of TBT

(Messing et al, 1997 ; Prasad & Schafran, 2006). More recent draft proposals

from EU legislation has seen this maximum allowable concentration fall to 1.5

ng L-1 and an average annual value of 0.2 ng L-1 (Commission of the European

Communities, 2006).

Similarly to permethrin, the environmental fate of TBT is to be adsorbed on to

sedimentary and particulate material, however it also has a tendency to de-sorb

when degraded to either dibutyltin or monobutyltin as they have less of an

adsorption capacity to particulates (Hoch & Schweisg, 2004). Due to this

capability of adsorption and de-sorption from sediments, TBT is ubiquitous

within the aquatic environment (Clark et al, 1988).

Within the environment, TBT will breakdown by a number of breakdown

pathways, these include direct photolysis, biodegradation and differing types of

chemical degradation (Clark et al, 1988). Of these degradation mechanisms

photolysis utilising natural light has been shown to be a slow method of

degradation with a half life of greater than 89 days and thus is not considered to

be a significant route (Clark et al, 1988). Of the three breakdown mechanisms

biodegradation is seen as the most significant (Clark et al, 1988), where it

degrades to dibutyltin, which will further degrade to monobutyltin, and finally

inorganic tin.

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There have been a number of studies on the removal of TBT in wastewater

treatment and in industrial wastewaters (mainly to do with the treatment of

shipyard wastes). In addition to this other authors have looked at the fate of

TBT in the wastewater environment.

Schafran and Tekleab (2000) and Schafran (2002) looked at various methods of

removing TBT from shipyard waters. These methods included

coagulation/clarification at a range of different pH’s (using both aluminium and

ferric sulphates as a coagulant at pH 6, 8, 10 and at doses ranging from 41-164

mg L-1 Al2(SO4)3 and 60-240 mg L-1 Fe2(SO4)3), granular media filtration,

granular activated carbon filtration (Calgon F400), and with UV/hydrogen

peroxide (No information on UV lamp intensity, and hydrogen peroxide

concentrations between 0 – 200 mg L-1). This study concluded that granular

media filtration had a poor affinity for removing TBT. The next least effective

method was coagulation/clarification with approximate removal rate of 45%.

Both granular activated carbon and UV/Hydrogen peroxide were assessed to be

effective methods for the removal of TBT from the shipyard wastewaters. Other

technologies for removal of TBT from industrial wastewaters include thermal

treatment at 1000ºC (Song et al., 2005) and sorption onto dolomitic sorbents

(Walker et al., 2005).

In wastewater treatment plants there have been a large amount of studies into

the occurrence of TBT, and its environmental fate and treatment. The

concentrations of TBT in the sewage treatment process influent range from

below the limit of detection of 1.8 ng L-1 (Donard et al., 1993) to 220 ng L-1 (Fent

& Mϋller, 1991; Fent 1996). A study by Fent in 1996 on organotin in municipal

wastewater in Switzerland showed 73% removal of organotins (including TBT)

in the primary effluent, this rose to 90% removal in the secondary effluent and

98% removal in the tertiary effluent. The major removal mechanism in this case

was adsorption onto the suspended solids in the wastewater treatment process.

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In this study Fent managed to map the mass balance of organotins throughout

the wastewater treatment plant (Figure 2.3):

2.5%

PC

AD

AS SC F

10%

90%

45%

48%

5%

22%

0.5%

5%

5%

Dissolved

Particulate

Key

122g/d = 100%

PC Primary Clarifier

AS Activated Sludge

SC Secondary Clarifier

F Filter

AD Anaerobic Digestion

Excess sludge 9.5%

Figure 2.3: Mass fluxes of total organotin through a wastewater treatment plant (From Fent, 1996).

Fent & Muller (1991) had earlier reported this removal percentage. In this earlier

study 92% of organotin was associated with the suspended solid fraction of the

wastewater treatment plant and this fraction was removed with the sewage

sludge. The incoming concentration of TBT ranged from 64-217ng L-1. Fent &

Muller concluded that adsorption into the sludge was the most important

process for organotin removal in sewage treatment. Biodegradation in the

activated sludge process only accounted for a 7.5% removal of the organotins.

Plagellat et al (2004) reported TBT levels in sewage sludge up to a maximum of

648.5 µg kg-1 dry weight confirming that TBT will preferentially associate itself

with the suspended solids within a wastewater treatment process.

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Once in the sludge fraction of sewage treatment a study by Fent et al., (1991)

showed that TBT was not significantly degraded. Whilst, Stasinakis et al. (2005)

reported removal of 99.7% of TBT with a degradation time of 10 days in

activated sludge and a sludge spiked at a concentration of 100 µg L-1 as Sn in

laboratory scale activated sludge batch reactors

2.2 Advanced Oxidation Processes & Adsorption

This study will look at four methods of removing permethrin and TBT from

wastewater. Three of these methods are advanced oxidation processes (AOP’s)

and are UV-Photolysis, UV-Photolysis combined with hydrogen peroxide and

hydrogen peroxide combined with ferrous sulphate, also know as Fenton’s

reagent. The fourth method of removal is adsorption onto granular activated

carbon (GAC).

UV-photolysis works on the principle of the absorption of UV light by a

compound in order to cleave the bonds of the compound. UV-

photolysis/hydrogen peroxide (UV/H2O2) and Fenton’s reagent both work on the

principle of generating the hydroxyl radical (HO•). The hydroxyl radical is one of

the most reactive free radicals and one of the strongest oxidants (Huang et al.,

1993) with only fluorine being more reactive (see table 2.2)

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Table 2.2: Oxidation potential of common species (Parsons, 2004)

Species Oxidation potential (V)

Fluorine 3.03

Hydroxyl radical 2.80

Atomic oxygen 2.42

Ozone 2.07

Hydrogen peroxide 1.78

Perhydroxyl radical 1.70

Permanganate 1.68

Hypobromus acid 1.59

Chlorine dioxide 1.57

Hypochlorus acid 1.49

Chlorine 1.36

2.2.1 UV-Photolysis

The underlying principle of UV-Photolysis of a target contaminant such as

permethrin and TBT, as in this study, is related to Planck’s law of radiation and

the laws of photochemistry, insofar as a certain amount of energy is needed for

the photon energy to match the bond energy and cleave the bonds within a

compound (Parsons, 2004).

The effectiveness of UV-photolysis is governed by the first law of

photochemistry which states:

“that only the light that is absorbed by a molecule can be effective in producing

a photochemical change in that molecule” (Parsons, 2004).

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This is measured by the Beer-Lambert law “which states that the fraction of light

absorbed by the system does not depend on the incident spectral radiant power

and the amount of light absorbed is proportional to the number of the

constituent molecules absorbing radiation” (Parsons, 2004). This gives us the

molar absorption coefficient of a pure compound at a given wavelength and

governs how much will be absorbed. This shows whether a compound will

absorb UV light and the energy required in order to cleave the compounds

bonds.

In this study the UV-C band range (between 200-280nm) specifically UV254 will

be used, as this is the wavelength where both the pollutants and the

constituents within the water absorb radiation (Parsons, 2004).

The most common reaction equations that a compound undergoes are below:

RX + hv → RX* (1)

RX* → (R• …•X) cage → R• + •X (2)

(R• …•X)cage → RX (3)

RX* → (R+ …X-) cage → R+ + X- (4)

RX* + O2 → RX+• + −

2O• (5)

RX* + 3 2O → RX + 1O2 (6)

(Parsons, 2004)

The excited state RX* is generated through light absorption processes in

equation 1, this is highly energetic and either deactivates to the ground state of

the molecule or undergoes “dark” chemical reactions, as in the equations above

(Parsons, 2004). The bond scission that occurs in equation 2 is the predominant

chemical pathway. Once the radicals have escaped from the solvent cage they

undergo further oxidation/reduction reactions depending upon the chemical

structure (Parsons, 2004).

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The effectiveness of UV-photolysis as a degradation technique for pesticides

has its limitations. In his review of pesticide chemical oxidation Chiron et al.

(2000), identified that pesticide degradation using an artificial light source

requires long treatment times of high energy photons and “rarely achieve a

complete degradation of the pollutant, ”with the exception of vacuum UV

(Chiron et al., 2000). However, in combination with other degradation

techniques, such as ozonation, Fenton’s reagent and hydrogen peroxide the

efficiency of these techniques can be greatly increased (Chiron et al., 2000).

Gogate & Pandit (2004) also identify that UV can be used in a photo-catalytic

oxidation to effectively degrade compounds in wastewater.

UV was used by Esplugas et al. (2002) to degrade phenol however a maximum

of 24% degradation was observed after 30 minutes of treatment at pH 4.4. This

decreased to 14% when the pH was increased to 6.8 and only 5% when the pH

was further increased to pH 11.5 due to a decreased quantum yield with

increasing pH. Esplugas et al. (2002) also concluded that the effectiveness of

UV increased when combined with another degradation technique such as the

use of hydrogen peroxide. The initial concentration of phenol ranged between

94 and 114 mg L-1 and the flux of radiation of the two ultraviolet lamps were

26.6 & 21.1 W m-2.

Experiments by Beltran et al. (1993) degraded atrazine in laboratory

experiments. Atrazine degradation using only direct UV photolysis had a half life

of between 3.5 – 11.7 minutes. When hydrogen peroxide was added to the test

solution the half life decreased 1.2-2 minutes. In the experiments using UV only

the concentration of atrazine ranged between 2.37 – 23.7 mg L-1 and the flux of

radiation from the ultraviolet lamp was 0.46 W m-2.

Fukui et al. (1991) managed to degrade up to 76% of 3-chloro-4-

(dichlormethyl)-5-hydroxy-2(5H)-furanone (MX) after a treatment time of 60

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minutes. This proves that the efficacy of UV-photolysis is very much dependant

upon the compound itself and the length of time that it is treated. In this study

only 1mL of 1mmol solution of MX was degraded under an 18W low pressure

mercury lamp at a path length of 30cm. Actinometric tests were not conducted

in order to determine the flux of radiation.

The table below summarises the experimental conditions and results of the

studies detailed:

Table 2.3: Experimental conditions of UV degradation case studies.

2.2.2 UV-Photolysis & hydrogen peroxide (UV/H2O2)

UV photolysis when combined with hydrogen peroxide has been studied in

conjunction with numerous industrial wastewater effluents especially the textile

industry, olive oil industry and the paper & pulp industries (Parsons, 2004).

The principle of UV/H2O2 is, as with all AOP’s, the production of the hydroxyl

radical. With this process the UV photolysis cleaves the hydrogen peroxide,

producing two hydroxyl radicals as in equation (7)

H2O2 + hv → OH• + OH• (7)

(Parsons, 2004)

Study Target compound

Initial concentration

UV Power % degradation

Esplugas et al. (2002)

Phenol 94-114 mg L-1

26.6 & 21.1 W m

-2 5-24% in 30 minutes (depending on pH)

Beltran et al. (1993)

Atrazine 2.37 -23.7 mg L-1

0.46 W m-2

99% in < 15 minutes

Fukui et al. MX 1mL of 1mmol

18W at a path length of

30cm

76% in 60 minutes

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The problem with UV/H2O2 is that the molar absorption coefficient is low. This

means that relatively high concentrations of hydrogen peroxide are required.

The disadvantage of this is that if the concentration is too high then hydrogen

peroxide scavenges the hydroxyl radical using the following reaction equations

(equations 8-10):

OH• + H2O2 → HO•2 + H2O (8)

HO•2 + H2O2 → OH• + H2O + O2 (9)

HO•2 + HO•

2 → H2O2 + O2 (10)

(Parsons, 2004)

In addition to this any alkalinity in the wastewater in the form of carbonate or

bicarbonate ions, also act as scavengers of the hydroxyl radical under the

following reaction equations (equations 11-12):

OH• + HCO3- → •CO3

- + H2O (11)

OH• + CO −2

3 → •CO3- + OH- (12)

The bicarbonate or carbonate ions react with part of the hydroxyl radicals to

form carbonate ion radicals, which although they do react with the organic

compounds, are much more selective and have lower rate constants (Parsons,

2004).

There have been a number of studies optimising the use of the UV/H2O2

technique on a variety of compounds and a variety of industrial and domestic

wastewaters as well as synthetic solutions on a laboratory scale.

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As mentioned earlier, a study by Beltran et al (1993) managed to degrade

atrazine with half life of between 1.2 – 2 minutes, apart from one sample where

hydrogen peroxide was added in excess and thus acted as a hydroxyl radical

scavenger (as in equations 8-10) and the half life increased to 7.2 minutes. In

total 99% of atrazine was removed. Concentrations of atrazine ranged between

3.8 x 10-5 and 9.6 x 10-5 mol L-1. The concentration of hydrogen peroxide used

ranged between 0.6 and 110 mmol L-1 and the UV incident flux radiation

0.52 W m-2.

Weir & Sundstrom (1993) looked at the degradation of trichloroethylene (TCE)

in phosphate buffer on a laboratory scale. This study looked at the kinetics of

TCE degradation and concluded that TCE reaction followed first order kinetics.

The UV intensity followed an apparent first order kinetic rate and the

concentration of hydrogen peroxide followed first order kinetics up to a

maximum level. The experimental conditions for these experiments were an

initial TCE concentration of 26.8 mg L-1, a hydrogen peroxide concentration

between 0.2mM and 20mM and a UV intensity between 0.8 and 2.88 W m-2. As

these experiments looked at the rate or reaction no details on how much TCE is

removed from solution is given.

A recent study by Yonar et al. (2006) applied UV/H2O2 to wastewater samples

and found over a 95% reduction in COD concentrations. This paper also

identified an approximate cost in terms of electrical energy per kg of COD of

10kWh. Experimental conditions for these experiments were an initial COD

concentration of 336 ± 25 mg O2 L-1, a hydrogen peroxide concentration

between 0.74 and 2.94 mmol L-1 and a UV intensity between 3 – 8.8 W m-2.


studies detailed:

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Table 2.4: Experimental conditions of UV/H2O2 degradation case studies.

2.2.3 Fenton’s reagent (Ferrous sulphate & hydrogen peroxide)

Fenton’s reagent generates the hydroxyl radical by a number of complex

chemical reactions, it was first used by Henry J Fenton in 1894 and further

developed by Haber & Weiss in 1934. It was not until 1949 that Barb et al.

proposed the following set of chemical reactions describing the “dark” reaction

of Fenton’s reagent (Pignatello et al., 2006):

Fe(II) + H2O2 → Fe(III) + OH- + HO• (13)

Fe(III) + H2O2 → Fe(II) + HO• 2 + H+ (14)

HO• + H2O2 → HO•2 + H2O (15)

HO• + Fe(II) → Fe(III) + OH- (16)

Fe (III) + HO•2 → Fe(II) + O2H

+ (17)

Fe (II) + HO•2 + H+ → Fe(III) + H2O2 (18)

HO•2 + HO•

2 → H2O2 + O2 (19)



H2O2 concentration

UV Fluence

% degradation

Beltran et al

(1993) Atrazine

8.2 – 20.7 mg L

-1 0.6–110 mmol L

-1

0.52 W m

-2 99%

Weir & Sundstrom

(1993) TCE 26.8 mg L

-1

0.2mM -20 mmol L

-1

0.8-2.8 W m

-2

No information

Yonar et al. (2006)

Wastewater 336 mg L-1 O2

0.74 – 2.94 mmol L

-1

3 – 8.8 W m

-2

95%

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In these reactions iron cycles between the +II and +III oxidation states where in

the absence of other oxidizable substances it acts as a catalyst to convert the

hydrogen peroxide to oxygen and water (Pignatello et al., 2006). The hydroxyl

radical is stoichometrically produced in reaction 1, but this produces a

stoichometric amount of Fe(III) which later precipitates as ferric oxyhydroxide,

as pH is increased, creating an undesirable sludge. In reaction 2 the generation

of the hydroxyl radical is catalytic in iron (Pignatello et al., 2006). Reactions 3 &

4 show the scavenging of the hydroxyl radical by both the hydrogen peroxide

and the ferrous iron, but, as iron is used catalytically this scavenging is kept to a

minimum, as is the production of ferric oxyhydroxide sludge. Although reaction

2 minimises the sludge production, it is also a lot slower in producing the

hydroxyl radical than reaction 1 (Pignatello et al., 2006).

The pH at which the Fenton’s reagent operates is vital to its effectiveness, as

this effects the species of iron present in solution, and thus the rate at which the

reaction progresses. Depending upon the target compounds, an ideal range for

the Fenton’s reactions is between pH 3-4, due to the formation of Fe(OH)2

which is approximately 10 times more reactive that Fe(II) (Pignatello et al.,

2006). Other authors have looked at the pH range and found that it is very much

target compound dependant and that this pH range can be extended to

approximately pH 5.5 (Arnold et al., 1995). Above pH 5.5, the effectiveness of

Fenton’s reagent declines rapidly due to the speciation of iron (Arnold et al.,

1995) and other compounds such as the bicarbonate ion, which is known to be

a strong scavenger of the hydroxyl radical (Beltran et al., 1993).

The degradation of a number of compounds such as atrazine, chloro-

benzenes, chloro-phenols & organo-phosphorus compounds, as well as the

treatment of domestic and industrial wastewaters with Fenton’s reagent, have

been studied in depth by a number of authors, although no studies on the

degradation of TBT or permethrin appear to have been performed.

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Arnold et al, (1993), have discovered the optimal conditions for atrazine

degradation using Fenton’s reagent showing that a pH of 3 and a 1:1 ratio of

2.69mM of FeSO4:H2O2 allowed a degradation of 30.2 mg L-1 of atrazine in

under 30 seconds. Gallard & De Latt in 2000 on kinetically modelled Fenton’s

like reactions using atrazine as a target compound showed that below a pH of 3

the degradation rate follows pseudo-first order kinetics. Atrazine was spiked at

a concentration of 0.15 mg L-1, a reaction pH of between 1 and 3 was used,

hydrogen peroxide concentrations between 0.2 mM and 1M and a ferric iron

concentration of 0.2mM. Gallard & De Latt in 2001 found that the kinetic

approach was much more complicated, with radical intermediates formed from

the decomposition of their target compounds reduced back to the parent

compound. This study used chlorobenzenes and phenyl-ureas as target

compounds at a concentration of 1µM, a reaction pH of 3, and an excess of

ferrous iron and hydrogen peroxide.

Badaway et al, (2006) compared the “dark” Fenton’s reactions (Fenton’s regent

without the addition of UV) with light enhanced Fenton’s reactions (i.e. the

addition of UV to Fenton’s reagent) and found that for organo-phosphorus

compounds the photo-assisted Fenton’s reactions were significantly more

efficient in wastewater, although the transitivity of the wastewater will have been

a factor on the efficiency of the degradation process. Initial concentrations of

organo-phosphorus pesticides were 50mg L-1, Fe2+ concentrations were

0.089mM and hydrogen peroxide concentrations were 8.99mM, the effect of pH

was studied with reaction pH’s between 2 & 5. This gave a 70% degradation in

a treatment time of 90 minutes.

Badaway & Ali in 2006 also studied the use of Fenton’s reagent in conjunction

with coagulation for industrial and domestic wastewater and found the

technique to very effective although quite expensive; however, this could be

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offset by lower consumption of disinfection chemicals. The experimental

conditions for this study were a COD concentration 1596 mg L-1 O2, pH 3, a

Fe2+ concentration of 400 mg L-1 and a hydrogen peroxide concentration of 550

mg L-1. This managed a COD reduction of greater than 90%.


studies detailed:

Table 2.5: Experimental conditions of Fenton’s reagent degradation case studies.

2.2.4 Adsorption

Adsorption can be simply defined as “the process of accumulating substances

that are in solution on a suitable interface” (Metcalf & Eddy, 2005). The

substance being removed from solution, the target compounds permethrin and

TBT, are the absorbates. Due to the high affinity of both permethrin and TBT to

be adsorbed by organic matter, or organic carbon as measured by their Koc

values (figures 2.1 & 2.2) adsorption is a viable alternative to advanced

oxidation processes for their removal from wastewaters.



H2O2 concentration

Iron concentration

% degradation

Arnold (1993)

Atrazine 30.2 mg L-1

2.69 mM L-1 2.69mM L

-1 100

Gallard & De Latt (2000)

Atrazine 0.15 mg L-1 0.2 mM L

-1 – 1

mol L-1 0.2mM L

-1

No information

Gallard & De Latt (2001)

Chloro-benzenes &

Phenyl-ureas

1µmol L-1 In excess In excess

No Information

Badaway et al.

(2006)

Organo-phosphorus pesticides

50 mg L-1 0.089 mM L

-1 8.99 mM L

-1 70

Badaway & Ali

(2006) Wastewater

COD: 1596 mg L

-1 O2

16.18 mM L-1

7.14 mM L-1 >90

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There have been numerous studies on the removal of both TBT from

wastewaters with adsorption (with a particular emphasis on GAC), as well as

conventional wastewater treatment processes (especially those wastes

produced by shipyards, where TBT concentrations can be as high as

1 mg L-1).

Schafran et al. (2001) reported the removal of TBT from shipyard waters

including adsorption on to GAC at both laboratory and full scale treatment. The

GAC chosen was Calgon F400. Schafran concluded that GAC adsorption

removed almost as much TBT as clarification and filtration and throughout the

entire treatment train, as much as 99.8% removal was observed, the capacity of

the Calgon F400 was not reported. Schafran did note in this study that there

maybe a small amount of TBT not being removed from the effluent due to the

presence of fine particulate TBT. The experimental conditions used in this study

were an adsorption time of 24 hours, a solution pH of 7.7, the GAC used was

Calgon F400 and at a quantity of between 0-4 g with volumes of water treated

of 0.75 L g-1, the initial concentration of TBT used was 4.08 mg L-1 in sonar

dome water

Schafran (2003) also reported the removal of TBT by GAC at laboratory and full

scale treatment processes in industrial wastewaters. This study discovered that

TBT was significantly adsorbed on to GAC where it could be degraded by

biological activity to dibutyltin, monobutyltin and eventually inorganic tin. The

biological activity contributed to the de-sorption of the tin species from the GAC

column as TBT was converted to mono or dibutyltin which desorbed from the

GAC. The GAC used was Calgon F400, a solution pH ranging between 5.5-8.5

to study pH effects on adsorption, TBT concentrations ranged between nothing

(to measure the amount of desorption) and 2mg L-1. No other experimental

conditions were available

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Prasad & Schafran in 2006 using a combination of coagulation-flocculation-

clarification and adsorption, managed to achieve 99.9% removal of TBT on a

full scale treatment basis, over 75% of the time, during a three year study. The

GAC contactor provided the best performance in the removal of TBT with 99%

of TBT entering the contactor being removed, however this removal was not

sufficient to bring concentrations to below regulatory levels of 50 ng L-1. The

experimental conditions used in these experiments were a flow of shipyard

wastewater at 190 L min-1 which had been adjusted to a pH of 7 and an initial

concentration of TBT ranging between 5.5 and 6260µg L-1. The dose and type

of GAC was not given

The removal of TBT using powdered activated carbon does not appear to have

been widely studied (although the study by Prasad & Schafran in 2006

mentions PAC, it is not expanded upon). This is also the case for permethrin

using adsorption processes where it does not appear to have been widely

studied.

Table 2.6: Experimental conditions of adsorption case studies.

2.3 Current study

From this literature review it can be concluded that:



GAC GAC concentration

% removal

Schafran et al. (2001)

TBT 4.08mg L-1

Calgon F400 0-4g

(0.75 L g-1)

99.9

Schafran (2003)

TBT 0-2mg L-1 Calgon F400 Not available

Not available

Prasad & Schafran (2006)

TBT 0.0055 - 6.26

mg L-1 Not available Not available 99.8

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• Studies have shown the toxicological effect of TBT, especially in

reference to its impact on oyster populations (Alzieu, 1991) and in

reference to its ability to cause imposex in the dog whelk (Yebra et al,

2004). Studies have also shown the toxicity of permethrin to the aquatic

environment especially its toxicity towards insect and invertebrate

populations (Kamrin, 1997) and also to fish populations (Sanchez-Fortun

& Barahona, 2005)

• The toxicity of TBT and permethrin to the aquatic environment, and their

presence within waste water treatment plant effluents, in high enough

concentration to cause environmental damage makes the study of their

removal necessary.

• Currently there is no active removal of either TBT or permethrin from

waste water treatment plants. Their removal is coincidental as they are

readily adsorbed onto the sewage sludge (Fent, 1996 ; Fent & Muller,

1991; Plagellat, 2004) and then the sewage sludge disposed of to land.

Despite this, concentrations at the effluent of wastewater treatment

plants are in high enough concentrations (Fent, 1996) to warrant the

need for further removal.

• Advanced oxidation processes and adsorption onto GAC have been

shown to be affective in the degradation of TBT (Schafran et al, 2001).

There appears to have been no studies to date on the removal of

permethrin using advanced oxidation processes or by adsorption.

As a result, this study will look at the removal of TBT and permethrin from

spiked de-ionised and wastewater treatment plant effluent using advanced

oxidation techniques and adsorption onto GAC.

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3.0 Objectives

The main objectives of this project were to:

• Evaluate the effectiveness of UV-photolysis, UV/H2O2 and Fenton’s

reagent to degrade permethrin and TBT in a deionised water and tertiary

wastewater matrix.

• Compare the removal efficiency in comparison to GAC.

• Evaluate the cost of each of the processes in treating a tertiary

wastewater matrix.

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• 4.0 Paper for publication

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THE REMOVAL OF PERMETHRIN AND TBT FROM WASTEWATER USING ADVANCED OXIDATION PROCESS AND ADSORPTION

O.J.Grievson & S.A.Parsons.

Centre for Water Sciences, Cranfield University, Cranfield, Bedfordshire,

MK43 0AL, United Kingdom.

Abstract Permethrin and TBT are a persistent problem in the aquatic environment with

annual environmental quality standard failures reported in the waterways and

coastal waters of the United Kingdom. Their presence has been reported in

wastewater treatment plant effluents, methods of their removal are required.

This paper examines the degradation of permethrin and TBT with three

advanced oxidation processes; UV-photolysis, UV/H2O2 and Fenton’s reagent.

The effectiveness and cost of each of the three processes is compared to

adsorption onto granular activated carbon (GAC).

UV/H2O2 was able to reduce permethrin and TBT simultaneously in water with

permethrin being removed to below the limit of detection and TBT removed to

89% of its initial concentration. UV-photolysis was able to remove both

permethrin in spiked deionised water but wasn’t as effective for TBT removal.

Fenton’s reagent wasn’t as effective as either of the photolysis methods for the

removal of the target compounds and adsorption, experimentally, wasn’t as

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effective as it should have been. This will be expanded upon in the results

section.

The final conclusion is that the cost of treatment was significant and for the

AOP’s predictions were £8.14 - £28.95 per m3 in comparison to treatment by

adsorption to GAC ranging between £0.02 – £0.07 per m3.

Keywords: Permethrin, TBT, UV-photolysis, wastewater, Fenton’s reagent.

4.1 Introduction

TBT and permethrin can be classed as two of many micro-pollutants present in

UK waters that cause problems in the natural environment. The toxicity of TBT

has been well documented especially its properties as an endocrine disruptor

and its previous impacts on the oyster industry (Alzieu, 1991). Permethrin is as

well documented and its effects on aquatic eco-systems can include

invertebrate and fish deaths (Kamrin, 1997).

The prevalence of both of these compounds meant that between 2003-2005

there were a total of 53 failures of environmental quality standards (EQS) in

freshwaters from TBT and 17 failures in freshwaters from a combination of

cyfluthrin and permethrin (Environment Agency, 2007).

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TBT has been legislated since 1982 as a result of damage to the oyster

industry, with a standard set at 20 ng L-1 (Alzieu, 1991) and later in the United

Kingdom in 1986 (Clark et al, 1998). Current proposed legislation as part of the

Water Framework directive in the proposed directive on environmental quality

standards in the field of water policy is to see the maximum allowable

concentration of TBT set to fall to 1.5 ng/L and an average annual concentration

of 0.2 ng L-1 (Commission of the European Communities, 2006).

Environmental quality standards for permethrin are set at a local level by the UK

Environment Agency and permethrin is classed as a dangerous substance

under the Dangerous Substance Regulations (Environment Agency, 2007).

Permethrin and TBT have been measured in wastewater treatment plants at

concentrations up to 81 µg L-1 for permethrin (Kupper et al, 2006) and

0.22 µg L-1 for TBT (Fent & Muller, 1991) their removal from the wastewater

treatment process is imperative in order to comply with the proposed UK and

EU legislation.

Whilst a number of major studies have reported that the major route of both

permethrin and TBT within the wastewater environment is to be adsorbed to the

solids and get captured within the sludge (Fent, 1996; Plagellat, 2004) however

this will not remove either compound in the liquid phased to below the proposed

European limit of 1.5 ng L-1 (Schafran, 2003).

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As a result of this, it is necessary to look at treatment methods for the removal

of both permethrin and TBT from wastewater. Due to both compounds high

affinity to be adsorbed the use of granular activated carbon (GAC) is a

possibility and has been studied previously (Schafran, 2003) and found to be

effective but not enough to remove TBT to below the regulated concentration of

50 ng L-1, in the shipyard waters that were studied. Due to the GAC’s inability to

reduce TBT to below the legislative limit Schafran also investigated the use of

UV/H2O2 advanced oxidation process and found it to be an effective process in

the removal of TBT from shipyard waters.

The aim of most advanced oxidation processes (AOP’s) is to produce the

hydroxyl radical in order to mineralise organic compounds to less toxic or ideally

harmless inorganic molecules (Parsons, 2004). In this study the advanced

oxidation process’s that are being used are UV photolysis in the UV-C

waveband at 254nm, a combination of UV photolysis and hydrogen peroxide

and finally Fenton’s reagent (a mixture of ferrous iron and hydrogen peroxide).

Their removal from tertiary wastewater streams either by degradation or by

adsorption onto GAC will be examined in terms of the effectiveness of the

techniques and their applicability to the wastewater industry.

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4.2 Materials & Methods

4.2.1 Reagents.

Permethrin (a mixture of cis & trans), TBT chloride, hydrogen peroxide (35%) &

sodium tetraethylborate were purchased from Sigma Aldrich. Ferrous sulphate

heptahydrate and n-hexane (Suprasolv grade) were purchased from VWR

International. Glacial acetic acid, sodium sulphate anhydrous, methanol, sodium

hydroxide & hydrochloric acid were purchased from Fisher Scientific. Apart from

the n-hexane which was of Suprasolv grade all chemicals purchased were of

analytical grade or better.

Mixed stock solutions of permethrin and TBT were prepared and stored in

amber glass bottles and stored at 4 ± 2ºC. Working solutions of permethrin and

TBT were prepared freshly from stock solutions. Sodium tetraethylborate

solutions (2% w/v) was prepared freshly as needed in a 25mL volumetric flask.

A 10% solution of glacial acetic acid was prepared in order to preserve all

sample/standard solutions (Readman & Mee, 1991).

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4.2.2 Samples

For the spiked deionised water degradation experiments (phase 1), working

solutions of permethrin and TBT were prepared freshly from stock solutions

using deionised water in a 5L volumetric flask to ensure sample

homogenisation.

For the spiked wastewater degradation experiments (phase 2), wastewater

effluent was taken from Cranfield University wastewater treatment works and

was spiked to the same concentration (0.51 µmol L-1 permethrin and TBT) as

used in the spiked deionised water degradation experiments.

4.2.3 Degradation experiments

4.2.3.1 Conditions for UV degradation experiments

The UV degradation experiments were conducted using a collimated beam

apparatus. The collimated beam apparatus delivered UV-C from 4 x 30 W low

pressure Wedeco NLR 2036 UV-lamps providing a total UV dose of

19.18 W m-2 at 254nm, UV dose was determined by Uridine actinometry.

The samples were degraded in an open petri dish under an automated shutter

beneath the UV source. Gentle stirring was provided by a magnetic stirrer so as

to mix the sample but not cause undue surface disturbance.

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The degradation experiments can be split into two phases:

4.2.3.2 Spiked deionised water degradation experiments

The spiked deionised water degradation experimental conditions can be found

in table 4.1 below:

1 litre of spiked deionised water was degraded for two hours with stirring, the

exception to this are the UV experiments where a 250mL volume of sample was

used and degraded separately for each time period. 100mL aliquots were taken

at 0, 20, 60 & 120 minutes. Once taken each sample was quenched with 10mL

of methanol and preserved with 0.1mL of 10% acetic acid (Readman & Mee,

1991).

The adsorption experiments used 250mL of sample and 0.25, 0.5, 1.25 & 2.5 g

of Norit 1240 GAC, and were shaken on a horizontal shaker for 24 hours. After

24 hours 100mL aliquots were taken and quenched with 10mL methanol and

preserved with 0.1mL 10% acetic acid (Readman & Mee, 1991). Samples were

then refrigerated at 4±2 ºC prior to ethylation (see section 4.2.4). Due to the fact

that the Norit 1240 GAC was not ground before the experiments Freundlich

constants of k and 1/n are unable to be calculated

4.2.3.3 Spiked wastewater degradation experiments

The experimental conditions for the spiked wastewater degradation experiments

can be seen in table 4.2:

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All experiments were conducted as per the spiked deionised water experiments

including sample quenching and preservation.

4.2.4 Ethylation/Extraction

All samples, standards and analytical quality control samples followed the same

ethylation procedure. Each 100mL aliquot was simultaneously ethylated with

0.5mL of 2% sodium tetraethylborate (Huang, 2004) and extracted into hexane

by shaking for ½ hour. The ethylated sample was then transferred to a

separatory funnel to allow the two phases to separate, at this point the water

fraction was discarded The hexane fraction was dried under a stream of

nitrogen gas and re-dissolved using 2 mL of hexane and analysed by GC-MS

(section 4.2.5). The drying of the hexane fraction was omitted for the spiked

deionised water experiments.

4.2.5 Instrumental

A 2mL fraction of each standard/samples was transferred to a GC-MS vial and

added to the GC-MS auto-sampler (Agilent model 7683B) it was then analysed

by GC-MS (Agilent model 6890N, MSD 5973).

The GC-MS was setup with the following conditions:

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Column: ZV-5HT Inferno (30m long, internal diameter of

0.25mm and a 5% phenyl- 95% polysiloxane film

thickness of 0.25µm). (Gomez et al, 2007)

Injection volume: 2µL.

Injection mode: Splitless.

Carrier gas: Helium.

Scan range: 40-550 amu.

Solvent delay: 4 minutes.

Injector temperature: 270ºC

Transfer line

Temperature: 300 ºC

The oven programme was set at 80ºC for the first two minutes and then ramped

at 30 ºC min-1 to a temperature of 210 ºC, and then ramped at 3 ºC min-1 to a

temperature of 270 ºC. The oven temperature was then held for 4 minutes at

270 ºC. The total programme lasted 30 minutes and 20 seconds (adapted from

Esteve-Turillias et al, 2006).

An example of the GC-MS chromatogram as produced by the GCMS is shown

below (figure 4.1)

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4.3. Results

This section will reveal the result of the method development of the GC-MS

method used for this study and discuss the results of the degradation

experiments including a comparison of the quantum yield, rate constants and

electrical energy per unit order (EEO) costs.

4.3.1 Method development

The simultaneous analysis of TBT and permethrin by GC-MS was developed

solely for this study, rather that the more typical analysis by a combination of

GC-ECD (for permethrin) (Lee et al, 2002) and GC-FPD (for TBT) (Michel &

Averty, 1991). As a result of this method development was undertaken to

establish limits of detection and reproducibility of the method. These were

Limit of detection

Permethrin 0.05 µg L-1

TBT 0.13 µg L-1

Reproducibility

Permethrin 8 µg L-1

TBT 13 µg L-1

The limit of detection was determined by multiplying by six times the standard

deviation of the measurement of three blank samples. The reproducibility was

of 109

determined by multiplying three times the standard deviation of the

measurement of three blanks and three samples (spiked to 0.51 µM permethrin

and TBT). It is noted that the reproducibility of the analysis of TBT could have

been improved by the addition of an internal standard of another organotin

compound, such as tripropyltin.

4.3.2 Control degradation experiments

In the de-ionised water and wastewater degradation experiments two types of

control experiments were undertaken using (1) Ferrous sulphate and (2)

hydrogen peroxide

Ferrous sulphate addition (concentration 0.3 mM and 3 mM at pH 3 & 5) gave a

maximum removal of 37 % removal of TBT and 28% permethrin at the lower

concentration of 0.3mM Fe(II) and up to 74% degradation at the higher

concentration of 3mM Fe(II). This was due to the high Kow of both compounds

and the formation of ferrous sulphate flocs. When flocs were formed both

compounds naturally adsorbed to the flocculated particles. Ferrous sulphate

degradation was not undertaken on the wastewater matrix.

Hydrogen peroxide in de-ionised water hydrogen peroxide gave removals of

permethrin and TBT ranging from 0% up to 50%. In wastewater, the hydrogen

peroxide degradation of permethrin and TBT was similar to that of de-ionised

of 109

water with maximum removal rates of 28% for permethrin and 46% for TBT. All

degradation experiments with hydrogen peroxide followed first order kinetics.

The control experiments, as was to be expected, showed generally lower

removal rates for both permethrin and TBT.

4.3.3 Direct & indirect photolysis

As both compounds have to be able to absorb UV light in order to be degraded

by UV-photolysis, experiments were undertake to establish the molar absorption

co-efficient of each compounds. This found that permethrin was highly

photolabile at a wavelength of 254nm and had a molar absorption co-efficient of

1332 M-1 cm-1 and TBT was not, with a molar absorption co-efficient of

3.3 M-1 cm-1, this compares to 500 M-1 cm-1 for 2-4 di-chlorophenol, 1300 M-1

cm-1 for NDMA and 4000 M-1 cm-1 for diazinon and atrazine (Sabhi & Kiwi, 2001;

(Sharlpless & Linden, 2003 ; Shemer & Linden, 2006; Stefan & Bolton, 2005).

Given the molar adsorption co-efficient for permethrin, it is not surprising that

degradation of permethrin, using just UV-photolysis, gave almost complete

removal with an 85% reduction with a dose of 2300 mJ cm-2. The addition of

H2O2 at this dose gave little improvement, but at the higher dose of 6900 mJ

cm-2 the concentration of permethrin fell to below the limit of detection (0.05 µg

L-1). The lack of improvement due to the addition of hydrogen peroxide, and the

generation of the hydroxyl radical, was due to the already high photolability of

of 109

permethrin. All of the degradation experiments with UV and UV/H2O2 follow

initial first order kinetics. This can be seen in figure 4.2

However for TBT the low molar absorption co-efficient means that the

degradation of TBT with UV-photolysis alone is poor with removal increasing

from 25% at a dose of 2300 mJ cm-2 to a maximum of 45% degradation with a

UV dose of 13800 mJ cm-2 (Figure 4.2). Once H2O2 is added the degradation of

TBT is markedly increased with a degradation of 58% at 2300 mJ cm-2 (0.3mM

H2O2) and 89% (3mM H2O2) at a dose of 13800 mJ cm-2. Degradation of TBT in

deionised water also follows initial first order kinetics

Permethrin degradation in wastewater is initially affected by the wastewater

matrix and the degradation after a dose of 2300 mJ cm-1 is greatly reduced to

that in deionised water especially with the higher concentration of 3 mM H2O2,

(Figure 4.3). However at a UV dose of 13800 mJ cm-2 both UV and UV/H2O2

reduce the concentration to below the limit of detection (0.05 µg L-1)

The degradation of TBT in wastewater exceeded the degradation in deionised

water. The mechanism that is involved was unknown but the quantum yield of

the reaction increased dramatically (ΦTBT in deionised water equalled 9 x 10-3

and in wastewater 2.4 x 10-2 an increase of approximately 20 times) as did the

rate constant, from that observed in deionised water (KTBT in deionised water

1.0 x 10-4 to KTBT in wastewater 1.1 x 10-3, this is an increase of over an order of

magnitude). The degradation by UV in wastewater, was greater than that by

of 109

UV/H2O2 at the lower concentration of 0.3mM H2O2 and equalled that of the

higher concentration of 3mM H2O2, with degradation by UV at a dose of 13800

mJ cm-2 equalling 99%, and with hydrogen peroxide addition 89% (0.3mM

H2O2) and 100% (below the limit of detection at 3mM H2O2). This can be seen

in figure 4.3.

4.3.4 Fenton’s reagent degradation experiments

The degradation of permethrin and TBT by Fenton’s reagent was not as

successful a treatment as UV & UV/H2O2. After a 120 minute degradation

period the most effective concentration of Fenton’s reagent (0.51:0.3mM

Fe(II):0.3mM H2O2) achieved a degradation of 73% of TBT at pH 3 (compared

to 37% removal for ferrous sulphate and 15% for H2O2) and 65% of permethrin

at pH 5 and the lower concentration of Fenton’s reagent (compared to 24%

removal with the ferrous sulphate and 28% removal with H2O2). Fenton’s

reagent at pH 5 was more successful at removing both compounds

simultaneously with a 54 % reduction in TBT and a 65 % reduction in

permethrin concentrations (compared with removal rates of 22% TBT and 24%

permethrin with ferrous sulphate and 46% TBT and 28% permethrin with H2O2.

of 109

4.3.5 Adsorption experiments

The Kow value of permethrin of log 6.1 and the Kow value of TBT of log 4.1

indicate that both permethrin and TBT should readily adsorb onto GAC. The

experimental results indicate that at a GAC concentration of 10g L-1 54% and

60% of permethrin is adsorbed to the GAC and 89 & 90% TBT was removed

from deionised and wastewater respectively (figure 4.5).

Permethrin adsorption in deionised water is more dependent on the dose of

GAC than TBT with removal ranging between 7% at a dose of 1g L-1 to 54% at

10 g L-1. In wastewater the removal of permethrin was 49% at a dose of 1 g L-1

and 66% at 10 g L-1.

TBT in wastewater removed 15% at 1 g L-1 and 90% at 10 g L-1. This can be

seen in figure 4.5

4.3.6 Rate constants, quantum yields & energy consumption

The processes evaluated here can be compared in terms of rate constants,

quantum yields and electrical energy required per order of degradation (EEO).

The rate constant has been calculated using the gradient of the degradation

and either calculated as a factor of time (s-1) or for the UV degradation in terms

of UV dose (cm2 mJ-1) and time (s-1).

of 109

The quantum yield has been calculated by comparing it to Uridine as a chemical

actinometer using the method as described in von Sonntag & Schumann

(1992).

The electrical energy required per order of degradation (EEO) has been

calculated using the method described by Bolton & Stefan (2002) and using the

following equation for a batch operation:

EEO (kWh m-3 per order) =

)log(

1000

f

i

C

CV

Pt

where:

P = power of lamp in kW (0.12) (personal communication, Wedeco)

t = time (hours)

V = volume of reactor (L)

Ci = initial concentration (mol L-1)

Cf = final concentration (mol L-1)

The values for the quantum yield, rate constants and EEO are shown below

(tables 4.3 & 4.4).

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4.4. Discussion

4.4.1 Mechanisms of degradation

In this study there were two mechanism for the degradation of permethrin and

TBT, namely the direct photolysis of our compounds with UV light at 254nm and

by the generation of the hydroxyl radical either by the photolysis of hydrogen

peroxide (indirect photolysis) or by Fenton’s reagent.

The degradation of any compound by direct and indirect photolysis is governed

by two parameters, the molar absorption co-efficient and the quantum yield of

the degradation.

The molar absorption coefficient is part of the Beer-Lambert law and states that

a compound must be able to absorb light in order for it to degrade. In this study,

permethrin had a high molar absorption coefficient (1332 M-1 cm-1) and was

significantly degraded by UV-photolysis. This is comparable to compounds such

as NDMA, simazine, atrazine, and diazinon which have molar absorption

coefficients higher than permethrin (1800, 3330, 3860, 4000 M-1

cm-1. Sharpless & Linden, 2003; Nick et al, 1992; Shemer & Linden, 2006) and

thus have quantum yields and high rate constants for degradation with UV-

photolysis (Table 4.5). Permethrin’s photolability means that it is readily

degraded by UV-photolysis.

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TBT degradation also demonstrated the Beer-Lambert law in deionised water.

The molar absorption co-efficient was very low, and as a result its degradation

was very poor, the quantum yield was also low, and thus there was very little

degradation. The generation of the hydroxyl radical was required by the

photolysis of hydrogen peroxide to degrade TBT. This can be seen for

compounds such as azo dyes (table 4.5) which are not significantly degraded

by UV light but are degraded when the hydroxyl radical is generated.

In wastewater the situation changed, permethrin degradation decreased due to

the matrix effects of the wastewater. Transitivity of UV decreased and thus the

direct photolysis of permethrin decreased, only when hydrogen peroxide was

added and the hydroxyl radical generated where the matrix affects counteracted

and degradation of permethrin occurred.

TBT degradation was quite different and it seemed that degradation by direct

photolysis was more efficient in wastewater than deionised water despite the

low molar absorption coefficient. The quantum yield of the reaction increased by

20 times and the rate constant by over an order, the mechanism of this reaction

was unknown. However, studies by Mailhot et al. (1999) using the photolysis of

the ferric iron to generate the hydroxyl radical is a reasonable mechanism for

the observed degradation of TBT in the wastewater matrix. In Mailhot’s study

ferric iron generated the hydroxyl radical via the following reaction:

of 109

Fe3+ + hv → Fe2+ + ●OH + H+

Although not measured it is reasonable to suggest that the tertiary wastewater

effluent from Cranfield University’s wastewater treatment plant would have iron

concentrations in the range that Mailhot used in his study (≈1.7 mg L-1). Thus,

what appeared to be the direct photolysis of TBT in wastewater was in fact the

photolysis of the ferric iron to generate the hydroxyl radical and degrade TBT by

indirect photolysis. The initial lag in the degradation was due to generation of

the hydroxyl radical by the ferric iron being slower than the generation of the

hydroxyl radical by hydrogen peroxide. The higher quantum yield and rate

constant of the reaction show that the UV/Ferric degradation was more efficient

at removing TBT that UV/H2O2. If the rate constant’s for UV/Fe(III) degradation

are compared for TBT only to the rate constants for Fenton’s reagent, it can be

seen that UV/Fe(III) is also more efficient that Fenton’s reagent, this suggests

that photo-Fenton’s or photo-Fenton like degradation processes maybe efficient

at removing TBT.

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4.4.2 Costs of treatment

The performance of each treatment process has been evaluated in terms of the

quantum yields, rate constants and also the electrical energy required per order

(EEo) of degradation. The calculated EEO for permethrin, 200 – 579 kWh per m3

and for TBT between 163 – 480 kWh per m3 (based on a wastewater matrix and

a UV dose of 2300 mJ cm-2). Based on a cost of £ 0.05 per kWh of electricity

this means that a 90% reduction in permethrin and TBT in the wastewater

matrix would cost approximately £8.14 - £28.95 per m3 of wastewater using

either UV or UV/H2O2.

This compares to £0.15 for compounds such as atrazine (Muller & Jekel, 2001)

and £1.50 for NDMA (Stefan & Bolton, 2002) in tap waters to approximately

£100 for some azo dyes in laboratory experiments with distilled water

(Muruganandham et al, 2007).

In comparison to this the price of using GAC to adsorb TBT and permethrin

would be approximately £0.02 - £0.07 per m3 of wastewater, this is based on an

initial cost per m3 of £1200 for Norit GAC 1240 and a regeneration cost

including the removal of GAC from site of £600 per m3 (Norit, 2007).

of 109

4.5. Conclusion

From the results of this study it can be concluded that:

• Amongst the AOP’s used in this study the most effective process used

was UV/H2O2 for the simultaneous removal of both permethrin and TBT

from wastewater based on the percentage removal of the compounds.

• Adsorption proved to be the most economical process with costs of

approximately £0.02 - £0.07 per m3 compared to £8.14 - £28.95 per m3

for removal using UV or UV/H2O2.

It can also be concluded that areas that require further study include

• Degradation products of the advanced oxidation processes needs to be

examined so as to ensure toxic by-products are not produced and that

the degradation to non-toxic by-products is complete.

• The effectiveness and economics of other AOP processes including, for

example, photo-Fenton’s reagent, especially considering the

effectiveness of UV/Fe(III) in the degradation of TBT.

of 109

• The use of other types of adsorbents to remove TBT and permethrin

from wastewater and an examination of the economics of this removal

process.

• The use of advanced oxidation processes and adsorption on un-spiked

wastewater samples and how effective these samples would be on a

wastewater treatment plant scale

4.6 Acknowledgements

I would like to acknowledge the support of United Utilities in the funding of this

project as part of the STAMP scheme.

of 109

4.7. References

Alzieu C, (1991), Environmental Problems caused by TBT in France:

Assessment, Regulations, Prospects, Marine Environmental Research, 32,

7-17.

Bhatkhande D, Kamble S, Sawant S, Pangarkar V, (2004) Photocatalytic and

photochemical degradation of nitrobenzene using artificial ultraviolet light,

Chemical Engineering Journal, 102, 283 – 290.

Bolton J, & Stefan M, (2002), Fundamental photochemical approach to the

concepts of fluence (UV dose) and electrical energy efficiency in photochemical

degradation reactions, Research on Chemical Intermediates, 28, 7-9.

Clark EA, Sterrit RM, Lester JN, (1988), The fate of TBT in the aquatic

environment: A look at the data, Environmental Science and Technology, 22(6),

Commission of the European Communities, (2006), Proposal for a directive of

the European parliament and of the council on environmental quality standards

in the field of water policy and amending directive 2000/60/EC, European

Parliament.

de Latt J, Gallard H, Ancelin S, Legube B, (1999), Comparative Study of the

oxidation of atrazine and acetone by H2O2/UV, Fe(III)/ H2O2/UV and Fe(III)/

H2O2, Chemosphere, 39 (15), 2693 – 2706.

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Environment Agency, Web reference http://www.environment-

agency.gov.uk/yorenv/eff/1190084/business_industry/agri/pests/917555,

accessed 15/08/07.

Esteve-Turrillas F, Pastor A, de la Guardia A, (2006), Comprison of different

mass spectrometric detection techniques in the gas chromatographic analysis

of pyrethroid unsecticide residues in soil after microwave-assisted extraction,

Analytical Bioanalytical Chemistry, 384, 801-809.

Fent K, (1996), Organo-tin compounds in municipal wastewater and sewage

sludge: contamination, fate in treatment process and eco-toxicological

consequences, The Science of the Total Environment, 185, 151-59.

Fent K, Müller MD, (1991), Occurrence of organotins in municipal wastewater

and sewage sludge behaviour in a treatment plant, Environmental Science and

Technology, 25, 489-93.

Gomez M, Martinez Bueno M, Lacorte S, Fenandez-Alba A, Aguera A, (2007),

Pilot survey monitoring pharmaceuticals and related compounds in a sewage

treatment plant located on the Mediterranean coast, Chemosphere, 66, 993-

1002.

Huang J, (2004), Reducing blank values for trace analysis of ionic organotin

compounds and their adsorption to different materials, International Journal of

Environmental Analytical Chemistry, 84(4), 255-265.

Kamrin M, (1997), Pesticide profiles: Toxicity , environmental impact and fate,

37-40, Lewis Publishers.

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Kupper T, Plagellat C, Brändli RC, de Allencastro LF, Grandjean D, Tarradellas

J, (2006), Fate and removal of polycyclic musks, UV filters and biocides during

wastewater treatment, Water Research, 40, 2603-12,

Lee S, Gan J, Kabashima J, (2002), Recovery of synthetic pyrethroids in water

samples during storage and extraction, Journal of Agricultural and Food

Chemistry, 50, 7194-7198.

Mailhot G, Astruc M, Bolte M, (1999), Degradation of TBT chloride in water

photoinduced by iron (III), Applied organometallic chemistry, 13, 53-61.

Michel P & Averty B, (1991), TBT analysis in seawater by GC FPD after direct

aqueous-phase ethylation using sodium tetraethylborate, Applied

organometallic chemistry, 5, 393-397.

Muller J, & Jekel M, (2001), Comparison of advance oxidation processes in flow

–through pilot plants (Part 1), Water Science & Technology, 44 (5),

303 – 309.

Muruganandham M, Selvam K, Swaminathan, (2007), A comparative study of

quantum yield and electrical energy per order (EEO) for advanced oxidative

decolourisation of reactive azo dyes by UV light, Journal of hazardous

materials, 144, 316-322.

Nick K, Scholer H, Mark G, Soylemez T, Akhlaq M, Schuchmannn H, von

Sonntag C, (1992), Degradation of some triazine herbicides by UV radation

such as used in the UV disinfection of drinking water, Journal of Water Supply

Research & Technology – Aqua, 41, 82-87.

Norit, (2007), Personal communication.

of 109

Parsons S, (2004), Advanced Oxidation Process for water and wastewater

treatment, IWA.

Plagellat C, (2004), Origines et flux de biocides et de filters UV dans les stations

dépuration des eaux , biblion.epfl.ch/EPFL/theses/2004/3053/EPFL_TH3053

.pdf

Readman J & Mee L, (1991), The reliability of analytical data for TBT (TBT) in

sea water and its implication on water quality criteria, Marine Environmental

Research, 32, 19-28.

Sabhi S, & Kiwi J, (2001), Degradation of 2,4-dichlrophenol by immobilized iron

catalysts, Water Research, 35 (8), 1994-2002.

Schafran G, (2003), Quarterly progress report for USEPA grant S-82874601-1:

Evaluate pilot and full scale treatment processes to remove TBT from industrial

wastewater, available at web reference: http://www.eng.odu.edu/casrm/tbt.htm

Shemer H, & Linden K, (2006), Degradation and by-product formation of

diazinon in water during UV and UV/H2O2 treatment, Journal of hazardous

materials, B136, 553 – 559.

Sharpless C, & Linden K, (2003), Experimental and Model comparisons of Low-

and medium- pressure Hg lams for the direct and H2O2 assisted UV

photodegradation of N-Nitrosodimethylamine in simulated drinking water,

Environmental Science & Technology, 37,1933 -1940.

Stefan M, & Bolton, (2002), UV Direct photolysis of N-Nitrosodimethylamine

(NDMA): Kinetic and Product study, Helvetica Chimica Acta, 85, 1416 - 1426.

of 109

Stefan M & Bolton, (2005), Fundamental approach to the fluence-based kinetic

and electrical energy efficiency parameters in photochemical degradation

reactions: polychromatic light, Journal of Environmental Engineering and

Science, 4, s13 - 18.

von Sonntag C & Schuchmann H, (1992), UV disinfection of drinking water and

by-product formation – some basic considerations, Journal of Water Supply

Research & Technology – Aqua, 41, 67-74.

of 109

4.8 Tables

Table 4.1: Experimental conditions for spiked deionised degradation experiments.

Degradation Conditions

Blank pH 3, 5, & 7

H2O2 pH 3, 5, 7 & 0.3 mM H2O2

pH 7 & 3 mM H2O2

Ferrous Sulphate pH 3, 5 & 0.3 mM Fe(II) pH 3, 5 & 3 mM Fe(II)

UV photolysis pH 7 & 19.18 W m-2

UV/H2O2 pH 7, 19.18 W m-2, 0.3mM H2O2 pH 7, 19.18 W m-2, 3mM H2O2

Fenton’s Reagent pH 3, 5 & 0.3 mM Fe(II) & 0.3 mM H2O2

pH 3, 5 & 3 mM Fe(II) & 0.3 mM H2O2

Adsorption pH 7 & 0,1,2,5,10 g L-1 Norit 1240 GAC

Table 4.2: Experimental conditions for spiked wastewater degradation experiments.

Degradation Conditions

Blank pH 7

H2O2 pH 7 & 0.3mM H2O2

pH 7 & 3mM H2O2

UV photolysis pH 7 & 19.18 W m-2

UV/H2O2 pH 7, 19.18 W m-2, 0.3mM H2O2 pH 7, 19.18 W m-2, 3mM H2O2

Adsorption pH 7 & 0,1,2,5,10 g L-1 Norit 1240 GAC

6 o

f 109

Table

4.3

: Table

of quantu

m y

ield

, ra

te c

onsta

nts

& E

EO v

alu

es for spik

ed d

e-ionis

ed w

ate

r experim

ents

Quantu

m Y

ield

R

ate

Consta

nts

E

EO

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

Spik

ed d

eio

nis

ed w

ate

r degra

dations

mol E

-1

mol E

-1

s-1

s-1

cm

2 m

J-1

cm

2 m

J-1

kW

h m

-3

kW

h m

-3

UV (1

9.1

8 W

m-2)

(pH

7)

9.0

0 x

10

-4

1.7

3 x

10

-2

1.0

4 x

10

-4

1.6

9 x

10

-3

1.2

9 x

10

-4

8.8

1 x

10

-4

1206

179

UV/H

2O

2

(19.1

8 W

m-2/0

.3m

M H

2O

2)

(pH

7)

1.0

0 x

10

-3

8.7

3 x

10

-2

3.2

7 x

10

-3

1.7

5 x

10

-3

3.1

4 x

10

-4

7.6

1 x

10

-4

515

216

UV/H

2O

2

(19.1

8 W

m-2/3

mM

H2O

2)

(pH

7)

2.4

4 x

10

-2

8.8

9 x

10

-2

6.0

3 x

10

-4

1.8

7 x

10

-3

4.0

4 x

10

-4

9.7

5 x

10

-4

402

169

Fento

n's

Reagent

( 0.3

mM

Fe(II), 0.3

mM

H2O

2)

(pH

3)

- -

1.9

9 x

10

-4

7.0

2 x

10

-5

- -

- -

Fento

n's

Reagent

( 0.3

mM

Fe(II), 0.3

mM

H2O

2)

(pH

5)

- -

1.4

8 x

10

-5

1.4

8 x

10

-4

- -

- -

Fento

n's

Reagent

( 3m

M F

e(II), 0.3

mM

H2O

2)

(pH

3)

- -

7.2

5 x

10

-5

4.8

5 x

10

-5

- -

- -

Fento

n's

Reagent

( 3m

M F

e(II), 0.3

mM

H2O

2)

(pH

5)

- -

5.3

4 x

10

-4

5.7

6 x

10

-5

- -

- -

7 o

f 109

Table

4.3

(continued): T

able

of quantu

m y

ield

, ra

te c

onsta

nts

& E

EO v

alu

es for spik

ed d

e-ionis

ed w

ate

r experim

ents

Quantu

m Y

ield

R

ate

Consta

nts

E

EO

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

Spik

ed d

eio

nis

ed w

ate

r degra

dations

mol E

-1

mol E

-1

s-1

s-1

cm

2 m

J-1

cm

2 m

J-1

kW

h m

-3

kW

h m

-3

Ferr

ous S

ulp

hate

(0

.3m

M F

e(II)) (p

H 3

) -

- 6.4

1 x

10

-5

6.7

3 x

10

-5

- -

- -

Ferr

ous S

ulp

hate

(0

.3m

M F

e(II)) (p

H 5

) -

- 1.6

8 x

10

-4

3.3

7 x

10

-4

- -

- -

Ferr

ous S

ulp

hate

(3

mM

Fe(II)) (p

H 3

) -

- 2.3

2 x

10

-4

8.1

9 x

10

-4

- -

- -

Ferr

ous S

ulp

hate

(3

mM

Fe(II)) (p

H 5

) -

- 9.8

2 x

10

-5

5.1

2 x

10

-5

- -

- -

Hydro

gen P

ero

xid

e

(0.3

mM

H2O

2) (p

H 3

) -

- 2.2

6 x

10

-5

9.6

1 x

10

-5

- -

- -

Hydro

gen P

ero

xid

e

(0.3

mM

H2O

2) (p

H 5

) -

- 1.3

3 x

10

-4

9.4

6 x

10

-5

- -

- -

Hydro

gen P

ero

xid

e

(0.3

mM

H2O

2) (p

H 7

) -

- -

1.4

4 x

10

-5

- -

- -

Hydro

gen P

ero

xid

e

(3 m

M H

2O

2) (p

H 7

) -

- 1.7

1 x

10

-4

- -

- -

-

Adsorp

tion *

(Norit G

AC

1840) (p

H 7

) -

- 0.8

0

3.7

x 1

0-2

- -

- -

* A

dsorp

tion in µ

M/g

GA

C

8 o

f 109

Table

4.4

: Table

of quantu

m y

ield

, ra

te c

onsta

nts

& E

EO v

alu

es for spik

ed w

aste

wate

r experim

ents

Quantu

m Y

ield

R

ate

Consta

nts

E

EO

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

TB

T

Perm

eth

rin

Spik

ed w

aste

wate

r degra

dations

mol E

-1

mol E

-1

s-1

s-1

cm

2 m

J-1

cm

2 m

J-1

kW

h m

-3

kW

h m

-3

UV

(19.1

8 W

m-2)

(pH

7)

2.4

4 x

10

-2

2.2

4 x

10

-2

1.1

0 x

10

-3

1.7

0 x

10

-3

5.6

2 x

10

-4

8.9

5 x

10

-4

163

238

UV/H

2O

2

(19.1

8 W

m-2/0

.3m

M H

2O

2)

(pH

7)

3.1

0 x

10

-3

2.3

1 x

10

-2

7.5

1 x

10

-4

1.7

5 x

10

-3

3.9

1 x

10

-4

9.1

5 x

10

-4

411

200

UV/H

2O

2

(19.1

8 W

m-2/3

mM

H2O

2)

(pH

7)

4.6

0 x

10

-3

8.6

5 x

10

-2

6.5

4 x

10

-4

3.4

4 x

10

-3

3.4

1 x

10

-4

8.9

6 x

10

-4

480

313

Hydro

gen P

ero

xid

e

(0.3

mM

H2O

2)

(pH

7)

- -

1.3

5 x

10

-3

8.2

8 x

10

-4

- -

- -

Hydro

gen P

ero

xid

e

(3 m

MH

2O

2)

(pH

7)

- -

1.1

2 x

10

-4

4.5

5 x

10

-4

- -

- -

Adsorp

tion *

(Norit G

AC

1840)

- -

3.6

x 1

0-2

5.8

x 1

0-2

- -

- -

* A

dsorp

tion in µ

M/g

GA

C

9 o

f 109

Table

4.5

: Q

uantu

m y

ield

s, ra

te c

onsta

nts

and E

EO v

alu

es o

f sele

cte

d c

om

pounds

Com

pound

Degra

dation

meth

od

Matr

ix

Quantu

m Y

ield

(m

ol E

-1)

K v

alu

e

(s-1)

EE

O

(kW

h m

-3)

Refe

rence

UV

254

Perc

hlo

ric a

cid

Spik

ed tap w

ate

r (E

EO

) 4.1

x 1

0-2

6.9

x 1

0-3

2.8

de L

att et al (1

999)

Mulle

r & J

ekel (2

001)

Atrazin

e

UV

254/H

2O

2

Perc

hlo

ric a

cid

Spik

ed tap w

ate

r (E

EO

) -

5.8

x 1

0-2

1.7

– 2

.3

de L

att et al (1

999)

Mulle

r & J

ekel (2

001)

UV

254

Aqueous s

olu

tion

2.4

x 1

0-2 –

4.1

x 1

0-2

8.0

x 1

0-4 –

1.3

x 1

0-3

14.4

- 2

3.6

R

eal et al (2

007a)

Dia

zin

on

UV/H

2O

2

Aqueous s

olu

tion

- 5.0

x 1

0-3

5.0

- 5

.2

Real et al (2

007a)

UV/H

2O

2

7 x

10

-3 -

3 x

10

-2

2.2

x 1

0-4

1666

Azo d

ye R

O4

Photo

-Fento

ns

Double

dis

tille

d w

ate

r 4.3

x 1

0-2 -

5.6

x 1

0-2

1.3

x 1

0-3

357

UV/H

2O

2

1.5

x 1

0-2

-

3.5

x10

-2

1.7

x 1

0-4

2000

Azo d

ye

RY14

Photo

Fento

ns

Double

dis

tille

d w

ate

r

6.3

x 1

0-2 -0.1

2

1.2

x 1

0-3

417

Muru

ganandham

et al

(2007)

UV

254

UV

200-3

00 (E

EO)

Sim

ula

ted d

rinkin

g

wate

r/

Dis

tille

d w

ate

r(E

EO)

0.3

2.7

x 1

0-3

0.3

- 2

9.6

Sharp

less &

Lin

den

(2003)

Ste

fan &

Bolton (2002)

N

DM

A

UV/H

2O

2

Sim

ula

ted d

rinkin

g

wate

r -

2.8

x 1

0-3

-

Sharp

less &

Lin

den

(2003)

of 109

4.9 Figures

Figure 4.1: Example chromatogram from the GC-MS (0.51µmol permethrin and

TBT in deionised water).

of 109

(a)

13800 mJ cm-26900 mJ cm-22300 mJ cm-2

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

(b)

2300 mJ cm-1 6900 mJ cm-113800 mJ cm-1

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

Figure 4.2: Permethrin (a) and TBT (b) reduction by UV and UV/H2O2 in spiked deionised water ( UV only 19.18 W m-2, UV/H2O2 19.18 W m-2/ 0.3mM H2O2, UV/H2O2 19.18 W m-2/ 3mM H2O2).

(a)

of 109

2300 mJ cm-1 6900 mJ cm-113800 mJ cm-1

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

(b)

2300 mJ cm-26900 mJ cm-2

13800 mJ cm-2

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

Figure 4.3: Permethrin (a) and TBT (b) reduction by UV and UV/H2O2 in spiked wastewater ( UV only 19.18 W m-2, UV/H2O2 19.18 W m-2/ 0.3mM H2O2, UV/H2O2 19.18 W m-2/ 3mM H2O2).

of 109

120 minutes60 Minutes20 Minutes0

10

20

30

40

50

60

70

80

90

100%

Reduction

Figure 4.4: Permethrin & TBT reduction by Fenton’s reagent in deionised water. ( TBT (0.3mM Fe(II) & 0.3mM H2O2, pH 3), TBT (0.3mM Fe(II) & 0.3mM H2O2, pH 5), Permethrin (0.3mM Fe(II) & 0.3mM H2O2, pH 3), Permethrin (0.3mM Fe(II) & 0.3mM H2O2, pH 5).

of 109

(a)

Deionised water Wastewater

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

(b)

WastewaterDeionised water

0

10

20

30

40

50

60

70

80

90

100

% R

eduction

Figure 4.5: Permethrin (a) and TBT (b) reduction by adsorption onto Norit GAC 1240 in spiked wastewater. ( 1 g L-1, 2 g L-1, 5 g L-1,

10 g L-1).

of 109

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wastewater treatment I: oxidation technologies at ambient conditions, Advances

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Kirk P, Rogers H, Lester J, (1989), The fate of chlorobenezenes and

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of 109

Appendix A : Methodology

of 109

A 1.1 Performance characteristics of the method

Substance determined Degradation of TBT and permethrin.

Type of sample Spiked deionised water and wastewater.

Basis of method Samples are degraded by a number of

methods, ethylated, extracted with hexane

and concentrations are measured by GC-MS.

Calibration curve Linear to within the scope of this method.

Limit of detection 0.13 µg L-1 TBT.

0.05 µg L-1 total permethrin.

Reproducibility 13 µg L-1 TBT.

8 µg L-1 total permethrin.

Bias High iron concentrations negatively interfere

with the determination of both TBT.

of 109

A 1.2 Principle

Samples are degraded using one of the following techniques:

• Photo-degradation (using UV-C light at 254nm).

• Hydrogen peroxide addition (at two different concentrations).

• Ferrous sulphate addition (at two different concentrations).

• Photo-degradation with hydrogen peroxide addition (at two different

hydrogen peroxide concentrations).

• Degradation by Fenton’s reagent (at two different ferrous sulphate

concentrations).

• Adsorption (with powdered activated carbon).

After degradation samples are ethylated with sodium-tetraethylborate

converting the TBT to tributylethhyltin and extracted into hexane. After

ethylation and extraction samples are analysed on a gas chromatograph mass

spectrometer in comparison to ethylated standard solutions.

of 109

A 1.3 Reagents

A 1.3.1 Permethrin stock solution (1mmol)

Dissolve 0.3913g of permethrin in 200mL methanol. Quantitatively transfer to a

1L volumetric flask, add 1mL of 10% acetic acid (1.9) and make up to the mark

with methanol. Transfer to a brown bottle and refrigerate at 4°C ± 2 °C.

A 1.3.2 TBT stock solution (1mmol)

Dissolve 0.3255g of TBT in 200mL methanol. Quantitatively transfer to a 1L

volumetric flask, add 1mL of 10% acetic acid (1.9) and make up to the mark

with methanol. Transfer to a brown bottle and refrigerate at 4°C ± 2 °C.

A 1.3.3 Permethrin working solution (0.51µmol)

Pipette 2.55mL of permethrin stock solution into a 5L volumetric flask. Add

500mL of water and mix. Make up to the mark with water and mix. This solution

should be prepared freshly just before use

A 1.3.4 TBT working solution (0.51µmol)

Pipette 2.55mL of TBT stock solution into a 5L volumetric flask. Add 500mL of

water and mix. Make up to the mark with water and mix. This solution should be

prepared freshly before use.

A 1.3.5 Mixed working solution (0.51µmol Permethrin & 0.51µmol TBT)

Pipette 2.55mL of Permethrin stock solution and 2.55mL of TBT stock solution

into a 5L volumetric flask. Add 500mL of water and mix. Make up to the mark

with water and mix. This solution should be prepared freshly before use. (for

stage 1 the water used should be deionised water, for stage 2 the spiking trial

the water should be a wastewater sample).

of 109

A 1.3.6 Mixed standard solutions

Standards of concentrations of 0, 0.15, 0.30, 0.45, 0.60µmol will be prepared.

Pipette 0, 0.015, 0.030, 0.045, 0.06mL of both permethrin stock solution (2.1.1)

and TBT stock solution (2.1.2) into a 100mL volumetric flask containing 20mL of

water. Mix to dissolve and make up to the mark with water. Prepare freshly

before use.

A 1.3.7 Sodium tetraethylborate (2% w/v)

Dissolve 0.5g of sodium tetraethylborate in 10mL of water. Quantitatively

transfer to a 25mL volumetric flask and make up to the mark with water. Store in

an amber bottle and refrigerate at 4°C ± 2°C. This solution will last two weeks.

A 1.3.8 Acetic acid (10% v/v)

Pipette 10mL of acetic acid (d20 1.05) into 40mL of deionised water in a 100mL

volumetric flask. Make up to the mark with water.

A 1.3.9 Hydrogen peroxide (10%)

Add 28.57mL of commercially purchased 35% hydrogen peroxide solution to a

100mL volumetric flask. Make up to the mark with water.

A 1.3.10 Ferrous sulphate solution (1% Fe)

Weigh 12.4452g of ferrous sulphate heptahydrate to a 200mL beaker. Add

200mL of water and dissolve. Quantitatively transfer to a 250mL volumetric

flask and make up to the mark with water.

A 1.3.11 Sodium hydroxide solution (0.1M)

Weigh 0.4g of sodium hydroxide pellets into a 200mL beaker. Add 50mL of

water and stir to dissolve. Transfer to a 100mL volumetric flask and make up to

the mark with water.

of 109

A 1.3.12 Hydrochloric acid solution (1M)

Pipette 8.6mL of concentrated hydrochloric acid (d20 1.18) into a 100mL of

volumetric flask containing 50mL of water, mix and make up to the mark with

water.

A 1.3.13 Hydrochloric acid solution (0.1M)

Pipette 10mL of hydrochloric acid (1.12) into a 100mL volumetric flask

containing 50mL of water. Shake to mix and make up to the mark with water.

A 1.4 Apparatus

Apparatus should be free from contamination before use. All apparatus should

be made from glass where possible.

A 1.4.1 Beakers, glass, nominal capacity 150mL

A 1.4.2 Beakers, glass, nominal capacity 400mL.

A 1.4.3 Beakers, glass, nominal capacity 2000mL.

A 1.4.4 Volumetric flask, glass, nominal capacity 25mL.





A 1.4.9 Separatory funnel, glass, nominal capacity 250mL.

A 1.4.10 Bottle, laboratory, glass, amber, nominal capacity 1000mL.

A 1.4.11 Bottle laboratory glass, amber, nominal capacity 150mL.

A 1.4.12 Stirring bar, glass, cylindrical

of 109

A 1.5 Procedure

A 1.5.1 Degradation.

This procedure should be used for stages 1 and 2 of the experimental

procedure. In stage 2 where a spiked wastewater is being used only the

relevant degradation procedures need to be used (i.e. each degradation

technique but only at optimal conditions).

Blank degradation experiments A 1.5.1.1 Quantitatively transfer 1L of mixed working solution (AP 1.3.5) to

three 2 litre beakers.

A 1.5.1.2 Using either sodium hydroxide solution (AP 1.3.11) or hydrochloric

acid solution (AP 1.3.13) adjust the pH of the beakers to pH 3, 5

or 7 using a calibrated pH meter.

A 1.5.1.3 Add a glass magnetic stirring flea and stir.

A 1.5.1.4 Quantitatively remove a 100mL aliquot from each beaker at 0

minutes, 20 minutes, 60 minutes & 120 minutes.

A 1.5.1.5 To each 100mL aliquot add 10mL of methanol and 0.1mL of 10%

glacial acetic acid solution (AP 1.3.8).

A 1.5.1.6 Transfer the preserved sample to a amber glass bottle

A 1.5.1.7 Label the sample and refrigerate at 4 ± 2ºC until ready for

ethylation (section AP 1.5.2).

of 109

UV degradation experiments

A 1.5.1.8 To a 400mL beaker add 250mL of mixed working solution (AP

1.3.5).

A 1.5.1.9 Irradiate with ultra-violet radiation using the collimated beam using

standard operating procedures for 0 minutes.


acid solution (AP 1.3.13) adjust the pH of the beaker to pH 7 using

a calibrated pH meter.

A 1.5.1.11 After irradiation take a 100mL aliquot.






A 1.5.1.15 Repeat steps 2.5.1.8 – 2.5.1.13 for irradiation times of 20 minutes,

60 minutes & 120 minutes.

Peroxide degradation experiments

A 1.5.1.16 Quantitatively transfer 1L of mixed working solution (AP 1.3.5) to

four 2 litre beakers.


acid solution (AP 1.3.13) adjust the pH of the beakers to pH 3, 5

or 7 using a calibrated pH meter. Adjust the fourth beaker to pH 7.

A 1.5.1.18 To the first three beakers (at pH 3,5 ,7) add 0.102mL of 10%

hydrogen peroxide solution (AP 1.3.9). To the fourth beaker add

1.02mL of 10% hydrogen peroxide solution (AP 1.3.9).

A 1.5.1.19 Add a glass magnetic stirring flea and stir each beaker on a

magnetic stirrer for 120 minutes.

of 109

A 1.5.1.20 At 0, 20, 60, 120 minutes remove a 100mL aliquot of solution from

each beaker.



A 1.5.1.22 Transfer the preserved sample to a amber glass bottle.



Ferrous sulphate degradation experiments

A 1.5.1.24 Quantitatively transfer 1L of mixed working solution (2.3.5) to four

2 litre beakers.

A 1.5.1.25 Using either sodium hydroxide solution (2.3.11) or hydrochloric

acid solution (2.3.13) adjust two of the beakers pH 3 and the other

two beakers to pH 5 using a calibrated pH meter.

A 1.5.1.26 Add a glass magnetic stirring flea and stir on a magnetic stirrer.

A 1.5.1.27 To the first two beakers (one at pH 3 and one at pH 5) add

1.675mL of ferrous sulphate solution (2.3.10). To the remaining

two beakers add 16.754mL of ferrous sulphate solution (2.3.10).


each beaker.


glacial acetic acid solution (2.3.8).




of 109

UV/H2O2 degradation experiments

Concentration A

A 1.5.1.32 To a 400mL beaker add 250mL of mixed working solution (2.3.5).

A 1.5.1.33 Add 0.026mL of 10% H2O2 (2.3.9) to the 250mL of mixed working

solution (2.3.5)





glacial acetic acid solution (2.3.8).




A 1.5.1.39 Repeat steps 2.2.1.32 – 2.2.1.39 for irradiation times of 20

minutes, 60 minutes & 120 minutes.

Concentration B

A 1.5.1.40 To a 400mL beaker add 250mL of mixed working solution (AP

1.3.5).

A 1.5.1.41 Add 0.255mL of 10% H2O2 (AP 1.3.9) to the 250mL of mixed

working solution (AP 1.3.5)







of 109



A 1.5.1.47 Repeat steps 2.2.1.40 – 2.2.1.47 for irradiation times of 20

minutes, 60 minutes & 120 minutes.

Fenton’s reagent degradation experiments

A 1.5.1.48 Quantitatively transfer 1L of mixed working solution (AP 1.3.5) to

four 2 litre beakers.


acid solution (AP 1.3.13) adjust two of the beakers pH 3 and the

other two beakers to pH 5 using a calibrated pH meter.

A 1.5.1.50 Add a glass magnetic stirring flea and stir on a magnetic stirrer.

A 1.5.1.51 To all four beakers add 0.102mL of 10% H2O2 (AP 1.3.9).

A 1.5.1.52 To two of the beakers (one at pH 3 and one at pH5) add 1.675mL

of ferrous sulphate solution (AP 1.3.10). To the remaining two

beakers at 16.754mL of ferrous sulphate solution (AP 1.3.10).


each beaker.






of 109

Adsorption experiments

A 1.5.1.57 Quantitatively transfer 250mL of mixed working solution (2.3.5) to

five 400mL beakers.

A 1.5.1.58 Add 0, 0.25, 0.5, 1.25, 2.5g of granular activated carbon to

successive beakers. This represents GAC concentrations of 0, 1,

2, 5, & 10 g L-1. Cover the beakers.

A 1.5.1.59 Shake on a shaking table for a period of 24 hours.

A 1.5.1.60 Remove a 100mL aliquot of solution from each container.






A 1.5.2 Ethylation

A 1.5.2.1 Using either sodium hydroxide solution (2.3.11) or hydrochloric

acid solution (2.3.13) adjust the pH of each preserved aliquot to

pH 5.

A 1.5.2.2 To each 100mL aliquot add 0.1mL of sodium tetraethylborate

(2.3.7), and 2 mL of hexane (2.3.14) and shake vigorously for 30

minutes.

A 1.5.2.3 For each of the preserved aliquots from each of the degradation

stage (2.5.1) and individually, quantifiably transfer one at a time to

a 250mL separatory funnel. Allow the hexane and water fractions

to separate. Once separated discard the water fraction.

A 1.5.2.4 Transfer the hexane fraction to a 100 mL beaker and dry with a

gentle stream of nitrogen gas.

of 109

A 1.5.2.5 Once dry add 2 mL of hexane (2.3.14) and re-dissolve any

precipitate. Transfer the re-dissolved precipitate to a vial for

instrumental analysis (2.5.3)

A 1.5.3 Instrumental analysis

A 1.5.3.1 Set up the instrument according to the manufacturer’s instructions. A 1.5.3.2 Set up the oven programme on the GC-MS as detailed in table

1.5.3.1 Table 1.5.3.1: GC-MS oven programme

Temperature Start time Finish time

80 °C hold for 2 minutes 0 2

Ramped at 30°C min-1 to 210°C 2 8.33

Ramped at 3°C min-1 to 270°C 8.33 26.33

270°C hold for 4 minutes 26.33 30.33

Set the injector temperature to: 270°C.

Injection volume: 2µL

Split/Splitless mode: Splitless

Transfer line temperature set to: 300°C.

Carrier gas: Helium.

Scan range: 40-550 amu.

Solvent delay: 4 minutes.

A 1.5.3.3 Prepare mixed standards solutions (AP 1.3.6), ethylate 100mL of

mixed standard using procedure AP 1.5.2.1-5 and inject into the

gas chromatograph-mass spectrometer. Check linearity of the

standard curve.

of 109

A 1.5.3.4 If the linearity of the standard curve is acceptable then continue to

run samples. If not then re-prepare standards and re-run. Within

each run include analytical control samples (blanks or spiked

samples) every 10 analytes.

A 1.5.3.5 Record all results.

A 1.6 Calculation

If the appropriate concentration factor is entered into the GC-MS then all results

should be directly read from the GC-MS output.

of 109

Appendix B: Uridine Actinometry

of 109

B 1.0 Aim

The aim of this experiment was to calibrate the collimated beam device in order

to ascertain the intensity of ultra-violet radiation by using Uridine as a chemical

actinometer.

B 1.1 Methodology

B 1.1.1 Principle

The degradation of uridine under ultra-violet light is measured using a UV

spectrophotometer at a wavelength of 262nm. The rate of degradation of uridine

is used to calculate the power of the ultraviolet light emitted from the collimated

beam.

B 1.1.2 Equipment

All glassware should be clean and free from contamination before use.

B 1.1.2.1 100mL volumetric flask, glass.

B 1.1.2.2 500mL volumetric flask, glass.

B 1.1.2.3 1Litre volumetric flask, glass.

B 1.1.2.4 Petri dish, glass, 18.5cm diameter and a 5cm depth.

B 1.12.5 Spectrophotometer capable of measuring at 262nm.

B 1.1.2.6 Cuvettes, quartz with a 10mm path-length.

B 1.12.7 Collimated beam capable of emitting UV-light.

of 109

AP 2.1.3 Reagents

B 1.1.3.1 Sodium di-hydrogen phosphate solution

Weigh 15.6g of sodium di-hydrogen phosphate di hydrate into a 200mL beaker,

add water (AP 2.1.3.5) and stir to dissolve. Quantitatively transfer to a 500mL

volumetric flask and make up to the mark with water (AP 2.1.3.5).

B 1.1.3.2 Di-sodium hydrogen phosphate solution

Weight 14.195g of di-sodium hydrogen phosphate into a 200mL, add water and

stir to dissolve. Quantitatively transfer to a 500mL volumetric flask and make up

to the mark with water (AP 2.1.3.5).

B 1.1.3.3 Phosphate buffer

Add 255mL of sodium di-hydrogen phosphate solution (AP 2.1.3.1) and 245mL

of di-sodium hydrogen phosphate solution (AP 2.1.3.2) to a 1litre volumetric

flask. Swirl to mix and make up to the mark with water (AP 2.1.3.5). Measure

the pH of this solution and adjust to pH 6.88 with the addition of 0.1M sodium

hydroxide or 0.1M hydrochloric acid as necessary.

B 1.1.3.4 Uridine stock solution

Weigh 0.18g of Uridine into a 100mL beaker, add water (AP 2.1.3.5) and stir to

dissolve. Quantitatively transfer to a 100mL volumetric flask and make up to the

mark with water (AP 2.1.3.5).

B 1.1.3.5 Water

Use laboratory grade deionised water.

of 109

B 1.1.4 Procedure

B 1.1.4.1 Prepare volume of phosphate buffer (2.3.3) spiked with uridine

solution according to the table below:

Table B 1.4.1: Phosphate buffer and Uridine solution volumes.

Volume of phosphate buffer (mL) Volume of Uridine solution (mL)

150 0.3

200 0.4

250 0.5

Transfer the phosphate buffer spike with uridine to a Petri dish.

B 1.1.4.2 Turn on the collimated beam, following standard operating

procedures and allow to warm-up for 30 minutes.

B 1.1.4.3 Calculate Tmax according to the following equation:

Tmax (sec) =

IntensityMeasured

41095.2 ×

B 1.1.4.3 Using a pipette transfer a volume of phosphate buffer spiked with

uridine to a quartz cuvette until the cuvette is around ½ full.

B 1.1.4.4 Measure the initial absorbance of the uridine solution at 262nm

water (AP 2.1.3.5) as a blank solution and record the result (A0).

Return the contents of the cuvette to the Petri dish.

of 109

B 1.1.4.5 Irradiate the sample for 1/3rd of Tmax. Transfer a volume of

phosphate buffer using a pipette to a cuvette until about ½ full.

Measure the absorbance at 262nm, record the result (A1). Return

the contents of the cuvette to the Petri dish.

B 1.1.4.6 Repeat step 4.5 another twice in order to record the absorbance readings

at 2/3rd

Tmax and at Tmax.

B 1.1.5 Calculations

B 1.1.5.1 Calculate the log of each reading divided by the initial absorbance

( e.g. 0

1logA

A)

B 1.1.5.2 Plot a graph of the calculated logarithms against exposure time.

B 1.1.5.3 Calculate T90 by extrapolating the plotted line to 1 negative

logarithm (a 90% reduction) and read off the time in minutes.

Alternatively this can be calculated using linear regression.

B 1.1.5.4 Calculate the actual intensity using the following equation:

E (W m-2) = 60 x

29500

90T

of 109

B 1.2 Results

Tmax was calculated as 24 minutes for these experiments based on the

estimated irradiance.

The four experiments undertaken were:

• 250mL phosphate buffer with a concentration of 14µM Uridine and

unstirred.


unstirred.


unstirred.


stirred.

B 1.2.1 250mL phosphate buffer with a concentration of 14µM Uridine and

unstirred.

The results of this experiment are in the table below and are graphically

displayed in the graph below:

Table B 1.2.1.1: Results of 250mL phosphate buffer, unstirred

Time (minutes) Absorbance (262nm) log (At/A0)

0 0.169 0.000

8 0.083 -0.309

16 0.037 -0.660

24 0.018 -0.973

of 109

y = -0.0406x

R2 = 0.9993

-1

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0

0 8 16 24 32

time (min)

log (A

t/A

0)

Figure B 1.2.1.1: Graph of 250 mL phosphate buffer, unstirred results

From the graph T90 can be calculated as 24.6 minutes and the intensity in watts per

square metre can be calculated as 19.96.


unstirred.



Table B 1.2.2.1 Results of 200mL phosphate buffer, unstirred


0 0.19 0.000

8 0.089 -0.329

16 0.049 -0.589

24 0.027 -0.847

of 109

y = -0.0361x

R2 = 0.9946

-1

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0

0 8 16 24 32

time (min)lo

g (A

t/A

0)

Figure B 1.2.2.1 Graph of 200 mL phosphate buffer, unstirred results

From the graph T90 can be calculated as 27.7 minutes and the intensity in watts

per square metre can be calculated as 17.75.


unstirred.



Table B 1.2.3.1: Results of 150mL phosphate buffer, unstirred


0 0.154 0.000

8 0.09 -0.233

16 0.051 -0.478

24 0.025 -0.790

of 109

y = -0.0318x

R2 = 0.9943

-1

-0.8

-0.6

-0.4

-0.2

0

0 8 16 24 32

time (min)

log (A

t/A

0)

Figure B 1.2.3.1: Graph of 150 mL phosphate buffer, unstirred results




stirred.



Table B 1.2.4.1: Results of 150mL phosphate buffer, stirred


0 0.155 0.000

8 0.085 -0.261

16 0.032 -0.690

24 0.019 -0.912

of 109

y = -0.039x

R2 = 0.9863

-1

-0.8

-0.6

-0.4

-0.2

0

0 8 16 24 32

time (min)

log (A

t/A

0)

Figure B 1.2.4.1: Graph of 200 mL phosphate buffer, stirred results



B 1.3 Conclusions

From this work it can be concluded that:

• The volume of phosphate buffer and thus its depth causes a significant

change in the intensity ultra-violet irradiance the solution receives.

• The stirring of the phosphate buffer using a magnetic stirrer causes a

drop in intensity of ultra-violet irradiance (a 0.78 W per m2 was recorded

in these experiments).

of 109

Appendix C: Raw data

6 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M

Sample (Spiked de-ionised)

TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

Sta

ndard

Bla

nk

0

0

0

0.0

0

0.0

0

0.0

0

0.0

0

0.1

5 µ

M L

-1

360681

20000

95102

0.1

8

0.0

8

0.1

1

0.1

0

0.3

0 µ

M L

-1

826240

53128

226767

0.4

1

0.2

0

0.2

7

0.2

5

0.4

5 µ

M L

-1

908613

103302

348684

0.4

5

0.3

9

0.4

2

0.4

1

0.6

0 µ

M L

-1

1479980

162378

539633

0.7

4

0.6

2

0.6

5

0.6

3

Bla

nk

170

140

150

0.0

001

0.0

005

0.0

002

0.0

003

Bla

nk

120

120

130

0.0

001

0.0

005

0.0

002

0.0

002

Bla

nk

135

120

125

0.0

001

0.0

005

0.0

001

0.0

002

Bla

nk

130

115

118

0.0

001

0.0

004

0.0

001

0.0

002

Spik

e

930005

109892

400735

0.4

6

0.4

2

0.4

8

0.4

6

Spik

e

987615

98227

352043

0.4

9

0.3

7

0.4

2

0.4

5

Spik

e

929136

110072

392250

0.4

2

0.4

7

0.4

8

0.4

7

Bla

nk d

egra

dation p

H 3

T0

1440468

148759

484257

0.7

2

0.5

7

0.5

8

0.5

7

Bla

nk d

egra

dation p

H 3

T20

1353878

127981

409249

0.6

8

0.4

9

0.4

9

0.4

9

Bla

nk d

egra

dation p

H 3

T60

1378444

122848

384201

0.6

9

0.4

7

0.4

6

0.4

6

Bla

nk d

egra

dation p

H 3

T120

1518004

142490

459234

0.7

6

0.5

4

0.5

5

0.5

4

Bla

nk d

egra

dation p

H 5

T0

1653541

94613

284905

0.8

3

0.3

6

0.3

4

0.3

4

Bla

nk d

egra

dation p

H 5

T20

1693260

96543

301395

0.8

5

0.3

7

0.3

6

0.3

6

Bla

nk d

egra

dation p

H 5

T60

1573254

116458

351507

0.7

9

0.4

4

0.4

2

0.4

2

Bla

nk d

egra

dation p

H 5

T120

1794193

112902

339760

0.9

0

0.4

3

0.4

1

0.4

1

7 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M


TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

Bla

nk d

egra

dation p

H 7

T0

1581013

77139

253459

0.7

9

0.2

9

0.3

0

0.3

0

Bla

nk d

egra

dation p

H 7

T20

1555646

139061

229584

0.7

8

0.5

3

0.2

8

0.3

4

Bla

nk d

egra

dation p

H 7

T60

1593258

92624

289975

0.8

0

0.3

5

0.3

5

0.3

5

Bla

nk d

egra

dation p

H 7

T120

1720334

131783

233667

0.8

6

0.5

0

0.2

8

0.3

4

Ferrous S

ulp

hate

(0.3

mM

) pH

3 T

0

223254

123637

411237

0.1

1

0.4

7

0.4

9

0.4

8

Ferrous S

ulp

hate

(0.3

mM

) pH

3 T

20

229391

120715

382710

0.1

1

0.4

6

0.4

6

0.4

6

Ferrous S

ulp

hate

(0.3

mM

) pH

3 T

60

183570

96478

323397

0.0

9

0.3

7

0.3

9

0.3

8

Ferrous S

ulp

hate

(0.3

mM

) pH

3 T

120

140756

86468

297054

0.0

7

0.3

3

0.3

6

0.3

5

Ferrous S

ulp

hate

(0.3

mM

) pH

5 T

0

184934

161093

524680

0.0

9

0.6

1

0.6

3

0.6

2

Ferrous S

ulp

hate

(0.3

mM

) pH

5 T

20

151183

108186

349307

0.0

8

0.4

1

0.4

2

0.4

1

Ferrous S

ulp

hate

(0.3

mM

) pH

5 T

60

144264

109332

351219

0.0

7

0.4

2

0.4

2

0.4

2

Ferrous S

ulp

hate

(0.3

mM

) pH

5 T

120

133516

127012

389096

0.0

7

0.4

8

0.4

7

0.4

7

Ferrous S

ulp

hate

(3m

M) pH

3 T

0

230044

117907

489042

0.1

2

0.4

5

0.5

9

0.5

5

Ferrous S

ulp

hate

(3m

M) pH

3 T

20

174064

107682

107682

0.0

9

0.4

1

0.1

3

0.2

0

Ferrous S

ulp

hate

(3m

M) pH

3 T

60

124278

33776

114435

0.0

6

0.1

3

0.1

4

0.1

3

Ferrous S

ulp

hate

(3m

M) pH

3 T

120

141272

35790

119810

0.0

7

0.1

4

0.1

4

0.1

4

Ferrous S

ulp

hate

(3m

M) pH

5 T

0

126323

30417

139347

0.0

6

0.1

2

0.1

7

0.1

5

Ferrous S

ulp

hate

(3m

M) pH

5 T

20

112286

27745

132067

0.0

6

0.1

1

0.1

6

0.1

4

Ferrous S

ulp

hate

(3m

M) pH

5 T

60

107467

56273

211434

0.0

5

0.2

1

0.2

5

0.2

4

Ferrous S

ulp

hate

(3m

M) pH

5 T

120

79148

50815

205403

0.0

4

0.1

9

0.2

5

0.2

3

8 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M


TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

3 T

0

417426

40000

116574

0.2

1

0.1

5

0.1

4

0.1

4

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

3 T

20

328845

35000

109261

0.1

6

0.1

3

0.1

3

0.1

3

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

3 T

60

266596

26793

116758

0.1

3

0.1

0

0.1

4

0.1

3

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

3 T

120

113548

26508

91554

0.0

6

0.1

0

0.1

1

0.1

1

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

5 T

0

372309

101558

343955

0.1

9

0.3

9

0.4

1

0.4

0

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

5 T

20

336590

86453

298150

0.1

7

0.3

3

0.3

6

0.3

5

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

5 T

60

283364

65409

247475

0.1

4

0.2

5

0.3

0

0.2

8

Fento

ns R

eagent (0

.3m

M F

e: 0.3

mM

H2O

2) pH

5 T

120

172564

29385

125718

0.0

9

0.1

1

0.1

5

0.1

4

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

3 T

0

999542

131118

445054

0.5

0

0.5

0

0.5

3

0.5

2

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

3 T

20

916214

97903

300194

0.4

6

0.3

7

0.3

6

0.3

6

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

3 T

60

775983

122314

359248

0.3

9

0.4

7

0.4

3

0.4

4

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

3 T

120

778700

100730

329600

0.3

9

0.3

8

0.4

0

0.3

9

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

5 T

0

819738

89460

277647

0.4

1

0.3

4

0.3

3

0.3

3

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

5 T

20

431911

98848

315058

0.2

2

0.3

8

0.3

8

0.3

7

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

5 T

60

296623

64968

234830

0.1

5

0.2

5

0.2

8

0.2

7

Fento

ns R

eagent (3

mM

Fe: 0.3

mM

H2O

2) pH

5 T

120

0

0

0

0.0

0

0.0

0

0.0

0

0.0

0

Hydro

gen P

ero

xid

e (0.3

mM

) pH

3 T

0

1923482

161658

540451

0.9

6

0.6

2

0.6

5

0.6

3

Hydro

gen P

ero

xid

e (0.3

mM

) pH

3 T

20

1944335

145235

503688

0.9

7

0.5

5

0.6

0

0.5

9

Hydro

gen P

ero

xid

e (0.3

mM

) pH

3 T

60

1773561

161857

546633

0.8

9

0.6

2

0.6

6

0.6

4

Hydro

gen P

ero

xid

e (0.3

mM

) pH

3 T

120

1634173

83159

267997

0.8

2

0.3

2

0.3

2

0.3

2

9 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M


TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

Hydro

gen P

ero

xid

e (0.3

mM

) pH

5 T

0

1619634

107568

372295

0.8

1

0.4

1

0.4

5

0.4

3

Hydro

gen P

ero

xid

e (0.3

mM

) pH

5 T

20

1380825

113871

398299

0.6

9

0.4

3

0.4

8

0.4

6

Hydro

gen P

ero

xid

e (0.3

mM

) pH

5 T

60

1353664

77532

263681

0.6

8

0.3

0

0.3

2

0.3

1

Hydro

gen P

ero

xid

e (0.3

mM

) pH

5 T

120

720176

89122

291449

0.3

6

0.3

4

0.3

5

0.3

4

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

0

563726

80624

251080

0.2

8

0.3

1

0.3

0

0.3

0

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

20

604906

96492

289190

0.3

0

0.3

7

0.3

5

0.3

5

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

60

626539

82935

257883

0.3

1

0.3

2

0.3

1

0.3

1

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

120

628753

67260

232855

0.3

1

0.2

6

0.2

8

0.2

7

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

0

816345

77995

253761

0.4

1

0.3

0

0.3

0

0.3

0

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

20

665233

85860

274268

0.3

3

0.3

3

0.3

3

0.3

3

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

60

496550

98835

301423

0.2

5

0.3

8

0.3

6

0.3

6

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

120

514604

57738

287574

0.2

6

0.2

2

0.3

4

0.3

1

UV

pH

7 T

0

1142845

118514

398797

0.5

7

0.4

5

0.4

8

0.4

7

UV

pH

7 T

20

849914

16000

51983

0.4

2

0.0

6

0.0

6

0.0

6

UV

pH

7 T

60

784927

8000

47800

0.3

9

0.0

3

0.0

6

0.0

5

UV

pH

7 T

120

623021

7000

40000

0.3

1

0.0

3

0.0

5

0.0

4

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

0

1889919

118483

364864

0.9

4

0.4

5

0.4

4

0.4

4

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

20

917019

30000

52000

0.4

6

0.1

1

0.0

6

0.0

8

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

60

837883

0

0

0.4

2

0.0

0

0.0

0

0.0

0

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

120

798126

0

0

0.4

0

0.0

0

0.0

0

0.0

0

00 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M


TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

0

1596216

131264

452203

0.8

0

0.5

0

0.5

4

0.5

3

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

20

630255

16000

45440

0.3

2

0.0

6

0.0

5

0.0

6

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

60

548968

0

0

0.2

7

0.0

0

0.0

0

0.0

0

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

120

171418

0

0

0.0

9

0.0

0

0.0

0

0.0

0

Adsorp

tion G

AC

1240 0

g/L

24 h

ours

1933373

70268

302161

0.9

7

0.2

7

0.3

6

0.3

3

Adsorp

tion G

AC

1240 1

g/L

24 h

ours

340537

67288

279934

0.1

7

0.2

6

0.3

4

0.3

1

Adsorp

tion G

AC

1240 2

g/L

24 h

ours

356645

64658

223652

0.1

8

0.2

5

0.2

7

0.2

6

Adsorp

tion G

AC

1240 5

g/L

24 h

ours

223043

44420

191811

0.1

1

0.1

7

0.2

3

0.2

1

Adsorp

tion G

AC

1240 1

0g/L

24 h

ours

206787

39509

131546

0.1

0

0.1

5

0.1

6

0.1

5

01 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M

Sample (Spiked wastewater)

TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

Bla

nk d

egra

dation p

H 7

T0

75696

36715

137412

0.1

1

0.9

4

0.7

4

0.7

9

Bla

nk d

egra

dation p

H 7

T20

22119

9355

37636

0.0

3

0.2

4

0.2

0

0.2

1

Bla

nk d

egra

dation p

H 7

T60

11434

13649

52777

0.0

2

0.3

5

0.2

8

0.3

0

Bla

nk d

egra

dation p

H 7

T120

14000

6500

17952

0.0

2

0.1

7

0.1

0

0.1

1

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

0

50655

79988

183570

0.0

7

2.0

4

0.9

8

1.2

6

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

20

31728

20383

75910

0.0

4

0.5

2

0.4

1

0.4

3

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

60

28956

13818

51715

0.0

4

0.3

5

0.2

8

0.3

0

Hydro

gen P

ero

xid

e (0.3

mM

) pH

7 T

120

10028

13131

49529

0.0

1

0.3

3

0.2

7

0.2

8

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

0

36000

21257

80435

0.0

5

0.5

4

0.4

3

0.4

6

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

20

36050

12408

46528

0.0

5

0.3

2

0.2

5

0.2

7

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

60

24095

10754

40615

0.0

3

0.2

7

0.2

2

0.2

3

Hydro

gen P

ero

xid

e (3m

M) pH

7 T

120

18241

6000

19216

0.0

3

0.1

5

0.1

0

0.1

2

UV

pH

7 T

0

484357

108695

371936

0.2

5

0.3

0

0.3

5

0.3

3

UV

pH

7 T

20

499971

28811

66135

0.2

6

0.0

8

0.0

6

0.0

7

UV

pH

7 T

60

10000

2000

2000

0.0

1

0.0

1

0.0

0

0.0

0

UV

pH

7 T

120

3800

0

0

0.0

0

0.0

0

0.0

0

0.0

0

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

0

950262

156933

472023

0.4

9

0..44

0.4

4

0.4

4

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

20

385983

29707

64593

0.2

0

0.0

8

0.0

6

0.0

7

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

60

124710

21717

35932

0.0

6

0.0

6

0.0

3

0.0

4

UV

/H2O

2 (0.3

mM

H2O

2) pH

7 T

120

108823

0

0

0.0

6

0.0

0

0.0

0

0.0

0

02 o

f 109

Abundance R

eadin

gs

Concentr

ation in µ

M

Sample (Spiked wastewater)

TBT

Cis Permethrin

Trans Permethrin

TBT

Cis

Permethrin

Trans

Permethrin

Permethrin

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

0

544878

124252

363182

0.2

8

0.3

5

0.3

4

0.3

4

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

20

250352

113824

145033

0.1

3

0.3

2

0.1

4

0.1

8

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

60

51807

0

0

0.0

3

0.0

0

0.0

0

0.0

0

UV

/H2O

2 (3m

M H

2O

2) pH

7 T

120

29257

0

0

0.0

2

0.0

0

0.0

0

0.0

0

Adsorp

tion 0

g/L

476550

73729

218121

0.2

5

0.2

1

0.2

0

0.2

0

Adsorp

tion 1

g/L

407400

53202

94855

0.2

1

0.1

5

0.0

9

0.1

0

Adsorp

tion 2

g/L

395130

50242

106250

0.2

0

0.1

4

0.1

0

0.1

1

Adsorp

tion 5

g/L

216680

21336

94687

0.1

1

0.0

6

0.0

9

0.0

8

Adsorp

tion 1

0g/L

45860

25707

73043

0.0

2

0.0

7

0.0

7

0.0

7

of 109

Appendix D: Water Research Guide for authors

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Guide for Authors 1. Submission All manuscripts should be submitted electronically through Elsevier Editorial System (EES) which can be accessed at http://ees.elsevier.com/wr. With the submitted manuscript authors should provide the names, addresses and e-mail addresses of four potential reviewers. Submission of a paper implies that it has not been published previously, that it is not under consideration for publication elsewhere, and that if accepted it will not be published elsewhere in the same form, in English or in any other language, without the written consent of the publisher. 2. Types of Contribution Papers are published either as a Full Paper or a Review Paper. Comments on these papers are also welcome. (a) A FULL PAPER is a contribution describing original research, including theoretical exposition, extensive data and in-depth critical evaluation, and is peer reviewed. The total length of a manuscript including figures, tables and references must not exceed 8000 words (40 pages). (b) REVIEW PAPERS are encouraged, but the Editor-in-Chief must be consulted beforehand, in order to decide if the topic is relevant. Only critical review papers will be considered. The format and length of review papers are more flexible than for a full paper. Review papers are peer reviewed. (c) COMMENTS on papers already published are welcome, subject to the criteria of interest, originality and the approval of the appropriate Editor. Comments can include extensions to, or criticisms of, those papers. They must provide arguments that are reasoned, and not presented in a confrontational fashion. They will be sent to the author of the original paper for reply, the outcome of which may be publication in a future issue. Comments and Authors' Replies should not exceed 1200 words each and will be received until 4 months after publication. They will be accepted or rejected without corrections.

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3. Paper Submission (a) All types of accepted submissions will have been peer reviewed. (b) Papers must be in English. Use professional help if English is not your mother tongue. Language Polishing: Authors who require information about language editing and copyediting services pre- and post-submission please visit

http://www.elsevier.com/wps/find/authorshome.authors/languagepolishing or contact [email protected] for more information. Please note Elsevier neither endorses nor takes responsibility for any products, goods or services offered by outside vendors through our services or in any advertising. For more information please refer to our Terms & Conditions http://www.elsevier.com/wps/find/termsconditions.cws_home/termsconditions (c) Manuscripts must be in double-spaced form with wide margins and line numbering. A font size of 12 pt is required. The corresponding author should be identified (include a Fax number and E-mail address). Full postal addresses (including e-mail addresses) must be given for all co-authors. Authors should consult a recent issue of the journal or the journal's website http://www.elsevier.com/locate/watres for style if possible. The Editors reserve the right to adjust style to certain standards of uniformity. (d) Multi-part papers are not to be considered. (e) Papers that are requested by the editors to be revised must be returned within 4 weeks or they will be regarded as withdrawn. (f) No page charges apply for Water Research. (g) The corresponding author, at no cost, will be provided with a PDF file of the article via e-mail or, alternatively, 25 free paper offprints (additional copies can be ordered at current printing prices). The PDF file is a watermarked version of the published article and includes a cover sheet with the journal cover image and a disclaimer outlining the terms and conditions of use. Additional copies can be ordered at current printing prices. (h) Submitted papers should be accompanied by a list of 4 potential referees with names and addresses.

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4. Content All pages must be numbered consecutively. Words normally italicised must be typed in italics or underlined. A manuscript would normally include a title, abstract, key words, introduction, materials and methods, results, discussion, conclusions and references. (a) Title page. The title page must state the names and full addresses of all authors. Telephone, fax and E-mail numbers must also be included for the corresponding author to whom proofs will be sent. (b) Abstract. Authors are requested to ensure that abstracts for all types of contribution give concise factual information about the objectives of the work, the methods used, the results obtained and the conclusions reached. A suitable length is about 150 words. (c) Key words. Authors must list immediately below the abstract up to 6 key words (not phrases) that identify the main points in their paper. (d) Abbreviations and Notations. Nomenclature must be listed at the beginning of the paper and must conform to the system of standard SI units. Acronyms and abbreviations must be spelled out in full at their first occurrence in the text. Authors should consult - Notation for Use in the Description of Wastewater Treatment Processes', Water Res. 1987;(21)2:135-9. (e) Conclusions. Papers must end with a listing of major conclusions, preferably in a list form. (f) References. References to published literature must be cited in the text as follows: Li and Gregory (2006) -The date of publication in parentheses after the authors' names.References must be listed together at the end of each paper and must not be given as footnotes. For other than review papers authors should aim to give no more than 20-30 recent, relevant references. They must be listed alphabetically starting with the surname of the first author, ( year ) followed by the title of the referenced paper and the full name of the periodical, as follows: Li, G. and Gregory, J. (2006) Flocculation and sedimentation of high-turbidity waters. Water Research 25(9), 1137-1143. It is particularly requested that (i) authors' initials, (ii) the title of the paper, and (iii) the volume, part number and first and last page numbers are given for each reference.

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References to books, reports and theses must be cited in the narrative. They must include the author(s), date of publication, title of book, editor(s) name(s) if applicable, page numbers, name of publisher, and place of publication. The abbreviation et al. may be used in the text. However, the names of all authors must be given in the list of references.Personal communications and other unpublished works must be included in the reference list, giving full contact details (name and address of communicator). Personal communications must be cited in the text as, for example, Champney (2006). References in languages other than English must be referred to by an English translation (with the original language indicated in parentheses). Citing and listing of web references. As a minimum, the full URL should be given. Any further information, if known (author names, dates, reference to a source publication etc.), should also be given. Web references can be listed separately (e.g., after the reference list) under a different heading if desired, or can be included in the reference list. The digital object identifier (DOI) may be used to cite and link to electronic documents. The DOI consists of a unique alpha-numeric character string which is assigned to a document by the publisher upon the initial electronic publication. The assigned DOI never changes. Therefore, it is an ideal medium for citing a document, particularly 'Articles in press' because they have not yet received their full bibliographic information. The correct format for citing a DOI is shown as follows (example taken from a document in the journal Physics Letters B): doi:10.1016/j.physletb.2003.10.071 When you use the DOI to create URL hyperlinks to documents on the web, they are guaranteed never to change. (g) Illustrations and Tables. The total number of all illustrations and tables should not exceed 10. If illustrations need to take up more space than 2 printed pages in Water Research (1 page for shorter contributions) the number of words must be reduced accordingly.All illustrations must be clear and of good quality. Scale bars should be used instead of magnifications, as these change if the photograph is reduced. Tables and their headings must be typed on a separate sheet. Type must be clear and even across columns. Particular care must be taken with nomenclature and sub- and superscripts to ensure correct alignment. Horizontal and vertical lines must be inserted to define rows and columns, and column headings must be correctly aligned.

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(h) Colour Illustrations: If, together with your accepted article, you submit usable colour figures then Elsevier will ensure, at no additional charge, that these figures will appear in colour on the web (e.g., ScienceDirect and other sites) regardless of whether or not these illustrations are reproduced in colour in the printed version. For colour reproduction in print, you will receive information regarding the costs from Elsevier after receipt of your accepted article. For further information on the preparation of electronic artwork, please see http://www.elsevier.com/artworkinstructions. Supplementary data Preparation of supplementary data. Elsevier accepts electronic supplementary material to support and enhance your scientific research. Supplementary files offer the author additional possibilities to publish supporting applications, movies, animation sequences, high-resolution images, background datasets, sound clips and more. Supplementary files supplied will be published online alongside the electronic version of your article in Elsevier Web products, including ScienceDirect: http://www.sciencedirect.com. In order to ensure that your submitted material is directly usable, please ensure that data is provided in one of our recommended file formats. Authors should submit the material in electronic format together with the article and supply a concise and descriptive caption for each file. For more detailed instructions please visit our artwork instruction pages at http://www.elsevier.com/artworkinstructions. 5. Proofs Corrections to proofs must be restricted to printer's errors. Please check proofs carefully before return, because late corrections cannot be guaranteed for inclusion in the printed journal. Authors are particularly requested to return their corrected proofs to Elsevier as quickly as possible to maintain their place in the printing schedule. 6. Transfer of Copyright Upon acceptance of a paper, authors will be asked to sign a Transfer of Copyright Agreement releasing copyright of the paper to Elsevier Ltd. Provision is made on the form for work performed for the United States Government (which is not subject to copyright restriction) and some United Kingdom Government work (which may be Crown Copyright). US National Institutes of Health (NIH) voluntary posting (" Public Access") policy Elsevier facilitates author response to the NIH voluntary posting request (referred to as the NIH "Public Access Policy"; see http://www.nih.gov/about/publicaccess/index.htm) by posting the peer-reviewed author's manuscript directly to PubMed Central on request from the author, 12 months after formal publication. Upon notification from Elsevier of acceptance,

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we will ask you to confirm via e-mail (by e-mailing us at [email protected]) that your work has received NIH funding and that you intend to respond to the NIH policy request, along with your NIH award number to facilitate processing. Upon such confirmation, Elsevier will submit to PubMed Central on your behalf a version of your manuscript that will include peer-review comments, for posting 12 months after formal publication. This will ensure that you will have responded fully to the NIH request policy. There will be no need for you to post your manuscript directly with PubMed Central, and any such posting is prohibited. If material from other copyrighted works is included, the author(s) must obtain written permission from the copyright owners and credit the source(s) in the article. Elsevier has preprinted forms for use by authors in these cases: contact Elsevier's Rights Department, Oxford, UK: phone (+44) 1865 843830, fax (+44) 1865 853333, e-mail [email protected]. Requests may also be completed online via the Elsevier home page http://www.elsevier.com/locate/permissions. Online Publication Your article will appear on Elsevier's online journal database ScienceDirect as an "Article in Press" within approximately 4-6 weeks of acceptance. Articles in Press for this journal can be viewed at http://www.sciencedirect.com/science/journal/00431354. An Article in Press may be cited prior to its publication by means of its unique digital object identifier (DOI) number, which does not change throughout the publication process. Reprints The corresponding author, at no cost, will be provided with a PDF file of the article via e-mail or, alternatively, 25 free paper offprints (additional copies can be ordered at current printing prices). The PDF file is a watermarked version of the published article and includes a cover sheet with the journal cover image and a disclaimer outlining the terms and conditions of use. Additional copies can be ordered at current printing prices. Author Discount Contributors to Elsevier journals are entitles to a 30% discount on most Elsevier books, if ordered directly from Elsevier. Author Enquiries For inquiries relating to the submission of manuscripts (including electronic submission where available) please visit http://www.elsevier.com/authors. The Elsevier Web page also provides the facility to track accepted articles and set up e-mail alerts to inform you of when an article's status has changed, as well as detailed artwork guidelines, copyright information, frequently asked questions, and more. Please note that contact details for questions arising after acceptance of an article (especially those relating to proofs) are provided after registration of an article for publication.

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