UNIVERSITI PUTRA MALAYSIA

DEGRADATION OF 2-CHLOROPHENOL IN WATER USING ADVANCED OXIDATION PROCESSES

LEONG JIN HOONG.

FK 2005 57

DEGRADATION OF 2-CHLOKOPHENOL IN WATER USING ADVANCED OXIDATION PROCESSES

BY

LEONG JIN HOONG

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in Fulfilment of the Requirements for the Degree of Master of Science

April 2005

Dedicated to mum, dad arrd pei clri~zg, with love

Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of the requirements of the degree of Master of Science

DEGRADATION OF 2-CHLOROPHENOL IN WATER USING ADVANCED OXIDATION PROCESSES

BY

LEONG JIN HOONG

April 2005

Chairman: Professor Azni Idris, PhD

Faculty: Engineering

The presence of endocrine disruptor chemicals (EDCs) in treated wastewater lately, is

alarming. Chlorophenols, an endocrine disruptor chemical compound is hardly

eliminated in water using conventional treatment. In this study, contaminated water

containing 2-Chlorophenol was treated using the Advanced Oxidation Processes

(AOPs) reactor (anolyte solution/ozone/UV) and anolyte solution alone. Various

conditions such as initial pH values, ozone dosages, reaction time and initial 2-

Chlorophenol concentrations were tested to achieve the optimum degradation of 2-

Chlorophenol. Possible intermediates and by-products in each treatment effluents were

investigated. Results showed that almost 90% of 2-Chlorophenol (5mgIL) degraded in

water with initial alkaline pH values (11-12) using AOPs reactor (anolyte solution

(O.4L)/Ozone 50% (0.5 1 mg/L)/UV). Complete (1 00%) degradation of 2-Chlorophenol

i n \i.ater was achieved when initial concentration of 2-Chlorophenol was 0.04 mg/L in

neutral pH condition. On the other hand, at least 70% of the ZChlorophenol degraded

when treated with anolyte solution in all initial pH values and initial 2-Chlorophenol

concentrations. Complete (100%) degradation of 2-Chlorophenol occurred when the

initial concentration of 2-Chlorophenol was 1.0 mg/L in original pH condition. All

effluent samples had acidic pH value except those 2-Chlorophenol solutions with initial

alkaline pH values. Comparison between two treatments showed that anolyte solution

was more effective to degrade 2-Chlorophenol than AOPs reactor at original and neutral

pH conditions. The degradation of 2-Chlorophenol compounds in water was achieved

up to 100% using anolyte solution compared to the AOPs reactor at higher 2-

Chlorophenol concentration in most cases. The 2-Chlorophenol degraded intermediates

and by-products using AOPs reactor and anolyte solution were mainly alkenes, alkanes,

carboxylic acid, ketones and ether functional group compounds.

Keywords: Degradaiion, 2-Chlorophenol, Advanced Oxidation Processses (A OPsj,

Abstrak yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Master Sains

DEGMDASI 2-KLOROFENOL DI DALAM AIR DENGAN MENGGUNAKAN PROSES PENGOKSIDAAN LANJUTAN

Oleh

LEONG JIN HOONG

April 2005

Pengerusi: Profesor Azni Idris, PhD

Fakulti: Kejuruteraan

Kehadiran bahan kimia gangguan endokrin di dalam air yang telah dirawat baru-baru ini

amat membimbangkan. Perawatan air yang konvensional tidak mampu untuk

menyingkirkan Klorofenol yang merupakan salah satu ahli kumpulan bahan kimia

gangguan endokrin. Dalam kajian h i , air buangan sintetik yang mengandungi 2-

Klorofenol telah dirawat dengan menggunakan proses pengoksidaan lanjutan

(kombinasi cecair 'anolyte'/ozon~lampu ultraungu) dan cecair 'anolyte' sahaja. Pelbagai

keadaan telah dikaji seperti nilai pH awal, dosej ozon, masa tindakbalas dan kepekatan

awal 2-Klorofenol untuk mencapai keadaan optimum degradasi 2-Klorofenol. Sampel

yang telah dirawat dari setiap proses perawatan tersebut dikenalpasti bahan perantaraan

dan degradasinya. Keputusan menunjukkan hampir 90% daripada 2-Klorofenol (SmglL)

di dalam air yang berkeadaan nilai pH awal beralkali (1 1-12) telah didegradasikan

dengan menggunakan reaktor proses pengoksidaan lanjutan (cecair 'anolyte' (0.4

L)/50% ozon (0.51 mglL)/lampu ultraungu). Degradasi 2-Klorofenol sepenuhnya

(100%) di dalani air dapat dicapai apabila kepekatan awal 2-Klorofenol berada pada

0.04 mg/L dalam keadaan nilai pH neutral. Sementara itu, sekurang-kurangnya 70% 2-

Klorofenol dapat didegradasikan apabila dirawat dengan menggunakan cecair 'anolyte7

di dalam semua keadaan nilai pH awal dan semua kepekatan awal 2-Klorofenol.

Degradasi 2-Klorofenol sepenuhnya (100%) di dalam air dapat berlaku apabila

kepekatan awal 2-Klorofenol berada pada I .O mg/L dalam keadaan nilai pH yang asal.

Sernua sampel yang telah dirawat oleh kedua-dua proses berada dalam keadaan berasid

kecuali sampel yang niiai pH pennulaannya beralkali. Cecair 'anolyte' didapati lebih

efektif dalam mendegradasikan 2-Klorofenol di dalam air berbanding reaktor proses

pengoksidaan lanjutan pada keadaan nilai pH asal dan neutral. Degradasi 2-Klorofenol

dapat dicapai 100% pada kepekatan awal 2-Klorofenol yang lebih tinggi oleh cecair

'anolyte' berbanding dengan menggunakan reaktor proses pengoksidaan lanjutan dalam

kebanyakan kes. Hasil bahan perantaraan dan degradasi yang telah dirawat oleh kedua-

dua proses tersebut terdiri daripada kumpulan berfungsi alkena, alkana, asid karbosilik

dan eter.

Kata kunci: Degmdasi, 2-Klorofenol, Proses pengoksidaan lanjutan, Cecair 'anolyte '

ACKNOWLEDGEMENTS

I would like to express my greatest gratitude to Prof Dr Azni Idris, for his kindness and

inspiration supervision during my master degree. I am here would like to take this

opportunity to congratulate Prof on behalf of his promotion as the first "Professor" in

the Department of Chemical and Environmental Engineering. Faculty of Engineering.

In deed, you are the best supervisor I had ever met.

Special thanks to Dr Katayon Saed. my co-supervisor for the distinguished research

guidance. I have learned much from you especially in writing manuscripts and research

findings. Dr, you have helped me a lot and it is not enough to just express in words.

Your hard work and dedication in research will be paid and appreciated.

Also to my girl friend Miss L,irn Pei Ching, your tenderness and care during my

research period is very much appreciated. Finally, to all my family members, friends

and colleagues, without you all, my life won't be meaningful in this world.

vii

I certify that an Examination Committee met on 29th April 2005 to conduct the final examination of Leong Jin Hoong on his Master of Science thesis entitled "Degradation of 2-Chlorophenol in Water Using Advanced Oxidation Processes" in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree) Regulations 1981. The Committee recommends that the candidate be awarded the relevant degree. Members of the Examination Committee are as follows:

Sa'ari Mustapha, PhD Associate Professor Faculty of Engineering Universiti Putra Malaysia (Chairman)

Fakhru'l-Razi Ahmadun, PhD Associate Professor Faculty of Engineering Universiti Putra Malaysia (Internal Examiner)

Robiah Yunus, PhD Lecturer Faculty of Engineering Universiti Putra Malaysia (Internal Examiner)

Zaini Ujang, PhD Professor Faculty of Engineering Universiti Teknologi Malaysia (External Examiner)

- -- -

School of Graduate Studies Universiti Putra Malaysia

This thesis submitted to the Senate of Universiti Putra Malaysia and has been accepted as fulfilment of the requirement for the degree of Master of Science. The members of the Supervisory Committee are as follows:

h n i Idris, PhD Professor Faculty of Engineering Universiti Putra Malaysia (Chaim~an)

Katayon Saed, PhD Lecturer Faculty of Engineering Universiti Putra Malaysia (Member)

AINI IDERIS, PhD Professor/Dean School of Graduate Studies Universiti Putra Malaysia

DECLARATION

i hereby declare that the thesis is based on my original work escepi fbr quotation and citations. which have been duly acknowledged. I also declared that it has not been previously or concurrently submitted for any other degree at UPM or other institutions.

I

LEONC ~1h HOONG

TABLE OF CONTENTS

Page

DEDICATION ABSTRACT ABSTRAK ACKNOWLEDGEMENTS APPROVAL DECLARATION LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS/NOTATIONS/GLOSSARY OF TERMS

CHAPTER

INTRODUCTION

LITERATURE REVIEW 2.1 Endocrine Disruptors Chemical (EDC) Issue 2.2 Sources of EDCs and Effects to Human, Wildlife and Environment 2.3 Chlorophenols as Endocrine Disruptor Chemicals (EDCs) 2.4 Sources of Chlorophenols in Environment 2.5 Chlorophenols as Disinfection By-products (DBP) 2.6 Physical and Chemical Properties of 2-Chlorophenol 2.7 Toxicity of 2-Chlorophenol 2.8 Chlorophenols Contamination Issue in Malaysia 2.9 Chlorophenols Degradation Technologies in Water and Wastewater

2.9.1 Physical Treatment 2.9.2 Biological Treatment 2.9.3 Chemical Treatment 2.9.4 Advanced Oxidation Processes (AOPs) Treatment 2.9.5 Advanced Oxidation Processes (AOPs) Hybrid System 2.9.6 Electrochemical Activation (ECA) 2.9.7 Application of Electrochemical Activation (ECA)

METHODOLOGY 3.1 Study Design 3.2 Preparation of 2-Chlorophenol Solutions 3.3 pH Adjustment of 2-Chlorophenol Solutions 3.4 First Experimental Set-up (Anolyte solution/03/UV)

3.4.1 30-Liter Reactor 3.4.2 Ozonator 3.4.3 UV Lamp 3.4.4 Spiral Collection Tank 3.4.5 Anolyte Solution Generated from the STEL-EC A

(Electrochemical Activation)

ii iii v vii viii X

xiii xv xvii

3.4.6 Experimental Setting 3.5 Second Experimental Set-up (Anolyte solution) 3.6 Chemical Analysis

3.6.1 Gas Chromatography with Flame Ionization Detector (GC-FI D) Analysis

3.6.2 Chlorophenol Calibration Curve 3.7 Identification of Intermediates and 2-Chlorophenol

Degradation Compounds 3.8 Data Analysis

RESULTS AND DlSCUSSION 4.1 First Experimental Set-up (Part 1): (Anolyte Solution/03/UV)

4.1. I Effects of Initial pH Condition 4.1.2 Effects of Reaction Time 4.1.3 Effects of Ozone Dosages 4.1.4 Statistical Analysis 4.1.5 Effects of Initial 2-Chlorophenol Concentration 4.1 -6 Recommendation 2-Chlorophenol Compounds Treatment

4.2 Second Experimental Set-up (Anolyte Solution) 4.2.1 Effects of Initial pH Condition 4.2.2 Effects of Initial Concentration of 2-Chlorophenol 4.2.3 Statistical Analysis

4.3 Identification of 2-Chlorophenol Degraded Intermediates and By-products 4.3.1 Using AOPs Reactor (Anolyte Solution/03/UV) 4.3.2 Using Anolyte Solution

CONCLUSION

REFERENCES

APPENDICES

BIODATA OF THE AUTHOR

xii

LIST OF TABLES

Table

Some sources and potential endocrine disruptor substances in our environment

European Endocrine Disruptors Research Inventory's "List of potential endocrine disruptors"

Commercial Productions and Application of 2-Chlorophenol Congeners

Physical and chemical properties of 2-Chlorophenol

Malaysian Standards Limit Effluent Discharged and National Water Quality Standards (Revised December 2000)

Summary of total phenolic concentration from different sources of eftluents discharged into the Sungai Langat River

Guidelines for chlorophenols standards limit in drinkin? water

Classification history of different UV ranges

Reactive ions and free radicals formed in the anolyte and catholyte solutions produced by electrochemical activation

Possibility of chemical reactions under electrochemical activation (ECA)

Specifications of the UV lamp

Specifications of the STEL-ECA system

First Experimental Setting (Anolyte solution/03/UV)

Second Experimental setting (Anolyte solution)

Column specifications and setting conditions used in GC-FID analysis

Recovery performance test

Column specifications and setting conditions used in GC-MSD analysis

Percentage lost of 2-Chlorophenol in AOPs reactor before treatment

pH values of influent and effluent samples during AOPs treatment

Experimental design to evaluate effects of 2-Chlorophenols initial concentrations

Page

6

4.4 Percentage lost of 2-Chlorophenol in I L beaker before treatment

4.5 Electrocliemical oxidation potential (EOP)

4.6 pH values of samples before and after treatment using anolyte solution

4.7 Selected samples for identification of 2-Chlorophenol degraded intermediates and by-products (GC-MSD analysis)

4.8 Possible 2-Chloropkenol intermediates and by-products i n the e ftlucnt samples after AOPs treatment

4.9 Possible 2-Chlorophenol intermediates and by -products in the eflluent samples after treatment using anolyte solution

LIST OF FIGURES

Figure Page

2.1 Resonance structures of ozone molecule

2.2 Mechanism of Ozone Decomposition - Initiation. Promotion, and Inhibition of Radical-Type chain Reaction

2.3 Primary reaction of ozone with a compound S

2.4 Range of electromagnetic waves

? 5 Regions of absorption of UV light -.-

3 I Summary of experimental design

3.2 Schematic diagram of the bench-scale AOPs reactor (side viewj

- -. 2.3 Schematic diagram of the bench-scale AOPs reactor (plan vieu~)

3.4 Schematic of STEL ECA System

3.5 Schematic diagram of second experimental set-up (Part 2)

4. i Effects of initial pH on 2-Chlorophenol degradation using anolyte solution (0.4 L)/Ozone 10% (0.15 mg/L)/UV

1.2 Effects of initial pH on 2-Chlorophenol degradation using anolyte solution (0.4 L)/Ozone 50% (0-5 1 mg/L)/UV

1.3 Effects of initial pH on 2-Chlorophenol degradation using anol9e solution (0.4 L)/Ozone 90% (0.88 mg/L)/UV

4-4 Effects of reaction time on 2-Chlorophenol degradation using anolyte solution (0.4 L)/Ozone 10% (0.15 mg/L)/UV

Effects of reaction time on 2-Chlorophenol degradation using anolyte solution (0.4 L)/Ozone 50% (0.5 1 mg/L)/UV

Effects of reaction time on 2-Chlorophenol degradation usins anolyte solution (0.4 L)/Ozone 90% (0.88 mdL)/UV

Effects of ozone dosages on 2-Chlorophenol degradation under 17.5 minute reaction time in AOPs reactor

4.8 Effects of ozone dosages on 2-Chlorophenol degradation under 19 minute reaction time in AOPs reactor

4.9 Effects of ozone dosages on 2-Chlorophenol degradation under 2 1.25 minute reaction time in AOPs reactor

4.10 Effects of ozone dosages on 2-Chlorophenol degradation under 25 minute reaction time in AOPs reactor

4.1 1 Comparison of 2-Chlorophenol degradation with different initial concentrations using AOPs reactor

4.1 2 Recommendation treatment

3.13 EtTects of initial pH values and initial concentration of 2-Chlorophenol on its degradation using anolyte solution

4.14a Possible 2-Chlorophenol degraded initial stage and pathway products using AOPs reactor

4. ! 4b Possible 2-Chlorophenol degraded intermediates and pathway products using AOPs reactor

4 . 1 3 ~ Possible 2-Chlorophenol degraded intermediates and pathway products using AOPs reactor

4.1 5 Possible 2-Chlorophenol degraded by-products and pathway products using anolyte solution

I l l

LIST OF ABBREVIATIONS

4-CP

AOPs

BDD

BOD

CAS

Clz

DBCP

DBP

DDE

DDT

DNA

ECA

EDCs

EEDRl

GC-FID

GC-MSD

HOCl

2,4,5-Trichlorophenoxyacetic acid

2,4-Dichlorophenoxyacetic acid

2.4-Dichlorophenol

2-Chlorophenol

4-Chlorophenol

Advanced Oxidation Processes

Boron-doped Diamond

Biological Oxygen Demand

Conventional Activated Sludge

Molecular Chlorine

Dibromochloropropane

Disinfection By-Products

Dichlorodiphenyldichloroethylene

Dichlorodiphenyltrichloroethane

Deoxyribonucleic Acid

Electrochemical Activatiott

Endocrine disruptor chemicals

European Endocrine Disruptors Research Inventory

Gas Chromatography-Flame ionization Detector

Gas Chromatography-Mass Spectrometric Detector

Hypochlorus Acid

HKT

oc1-

OI

PC I'

PVC

RO

SBR

S-N-K

SPE

TOC

UPUM

USEPA

uv

WHO

High Performance Liquid Chromatography

Hydraulic Retention Time

International Agency for Research on Cancers

Dissociation Constant

Parti tion Coefficient

Normal Standard Hydrogen Electrode

Hypochlorite Ion

Oxidation Index

Pentachlorophenol

Polyvinyl Chloride

Reverse Osmosis

Sequencing Batch Reactor System

Student-Newman-Keuls

Solid Phase Extraction

Total Organic Carbon

Unit Perundingan Universiti Malaya

United States Environmental Protection Agency

Ultraviolet

World Health Organization

CHAPTER 1

INTRODUCTION

Water is essential to every living thing on earth. Water can be mean of life or dead. In

some places, water is abundant while others water shortage is likely to occur. Today,

there are approximately 1.2 billion people are lack of access to safe water consumption

and 3 billion have insufficient sanitation (Ashraf, 2003). Thus, water is valuable and

some even naming water as "Blue Gold" where water is scarcely found. Despite water

is cost free and natural gifts, most of us taken for granted and our activities have

violated water causing severely water pollution. Those impurities in the water are wide-

ranging from substantially nutrient to heavy metal and eventually organic compounds.

The discovery of endocrine disruptor chemicals (EDCs) in the treated wastewater lately

is being concerned. EDCs compounds sources are mainly from the synthetic chemicals,

which have the ability to disrupt the healthy endocrine systems. Most of the EDCs

compounds are xenobiotic and complex organic compounds. They are highly toxic and

persistent to environment. Chlorophenols such as 2-chlorophenol (2-CP), 4-

chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) are

categorized as one of the group compounds belong to EDCs and have been named as

priority pollutants by the USEPA (Rao et al., 2003). The stability of the C-CI bond in

halohydrocarbons is responsible for their toxicity and persistence in the biological

environment (Rao et al., 2003).

The intrusion ol' 2-Chlorophcnol to the aquatic environment via various of discharges

fi-om psoducti(m of higher chlorinated phenols plants manufacturing. paper-mills as by-

product of chlorine-based bleaching. disinfection of sewage industrial wastewater with

chlminc. b\-prohcts as a results of slow microbial breakdown of herbicides and coal

e\trrtction iiidustries (Rao et al., 2003).

I n Malajsia. con~aniination of phenolic compounds is found in the rivers and streams.

Rc.centl!- OI'UM (2003) reported that most of the wastewater discharged from

Indi~iiries along the Sungai I-angat River is polluted with phenolic compounds. This

xrrste\\\.:iter cmtained extensively phenolic compounds, which is exceeded the standard

. . ii~nils (0.001 mg!L - Standard A) of environmental regulations. ihose highly toxic

coml?ounds are consequently harniful to humans, animals, and fish once they entered to

the ri\ws md streams.

Iience. in this critical environment, the conventional treatment such as biological

treatment is hardly eliminating those impurities (Papadaki et al., 2004). Thus.

formation of new treatment must fulfill at least the initial requirement, which is to

degrade those compounds into simplified ones is vital, in order to maintain the entire

\\ater bodies into a sustainable environment. The emergence of Advanced Oxidation

J'rocesses (AOPs) treatment are believed to be effectively against these intractable

compounds (Shu and Chang, 2005).

In this study, 2-('l~loroplienol is selected as surrogate EDCs compounds and spiked into

distilled uater as contaminated water. Ivhich then treated using AOPs. The objecti\ es of

the research are:

1. To evaluate thc possible degradation of 2-Chlorophenol using AOPs reactor:

which consisted of anolyte solution, ozone and UV lanip and to deterniiiie the

optimum condition for 2-Chlorophenol dezradation considering parameter such as

initial pH values, ozone dosages, reaction time and initial 2-Chlorophenol

concentrations.

2. To evaluate the possible degradation of 2-Cliloroplienol using anol~te du t ion

altwe arid to determine the influence of the initial pH kalue and initial 2-

Chloroplienol concentrations on degradation efficiency.

3. To idcntify the by-products of the reaction and to propose pathway of 2-

Chlorophenol degradation in water after each treatment.

CHAPTER 2

LITERATURE R E V I E l f

2.1 Endocrine Disruptor Chemicals (EDCs) Issue

The endocrine sjrstern consists of a set of glands that conlmunicates in a more diffuse

fashion. transporting information through the circulation from one tissue to another via

chemical messengers or hormones (Witorsch. 2002). These cheniicals messenger or

i~orrnones heip to guide the development. gro\\th. reproduction, and behavior of animals

i tx l i~ i f iny hunia:i hcings. Some of the endocrine glands include all iniportant functions

of an orgal;ism. suc!i as the pituitarq., tlqroid. and adrenal glands. the fernale ovaries

and male testes.

Endocrine disruptors are delined as " an exogenous substance or a mixture, that alters

functions of the endocrine system and consequently causes adverse health effects in an

intact organisni. or its progeny or (sub) populations"(European Commission, 1996).

Endocrine disruptior! refers to the interference of endocrine system function by

environmental chemicals. Endocrine disruptors may interfere with the normal

functioning of hormones in several ways. Ordinarily, a hormone binds exclusively to its

receptor on or inside a cell, like a key fitting into a lock. It then activates a chain of

events that results in a biological response. They act by modulating the levels of,

responses to hormones. These effects can be induced acc0rdin.g to various niechanisms

(Clan son. 2000).

An cndocrine-disruptitlg substance. however. may be shaped enough like the hornione

to bind to i ts rccepror. There. it may activate the receptor. initiating the chain of events

as if thc horinonc \vcrc there. Or it may simply occupy the hormone's usual binding

site. preventing normal hormone activity. Endocrine disruptors may also interfere with

.reru:n hornlone-binding proteins that regulate the availability and activity of hormones.

T!xy may chan~c the number of hormone receptors present in specific tissues, the

amount of a hornione produced, or the rate at which hormones are broken d o ~ n and

e~ct-eted. i n summal?. these substances augment, prevent, or otherwise alter the normal

a& ity of hormones.

To date. most research on endocrine disruption has tocused on synthetic chemicals that

perturb the normal activity of estrogens, androgens, and thyroid hormones, but some

chemicals disrupt other hormonal pathways as we1 I. Some sources and potential

endocrine disruptor substances in our environment are shown in Table 2.1.

Table 2.i Some sources and potential endocrine disruptor substanccs in our environment (Environment Canada. 1999)

- -

Son rces Category Substances (Uses)

Incineration, !,andfill

Agricultural runctff~atrnosplieric transport

Agl-icultural runoff

Harbours

Industrial and municipal eft1 uents

Industrial effluent

Municipal effluent and agricultural runoff

Pulp mill effluents

Polychlorinated conlpounds (from industrial production or by- products

of mostly banned substances)

Organochlorine pesticides (Found in insecticides, many

now phased out)

Pesticides currently in use

Organotins (found in antifoulants used to paint the hulls of ships)

Alkylphenolics (Surfactants - certain kinds of detergents used for removing oil - and their metabolites

Polychlorinated dioxins.

Polychlorinated biphenyls

DM. dieldrin, lindane

Alrazine, tri tluralin. perniethl-in

Nonylphenol

Phthalates (found in plasticizers) Dibutyl phthalate. hutylbenzyl phthalati

Natural Honnones (produced naturally by animals);

Synthetic steroids (found in contraceptives)

Phytoestrogens (Found in plant material)

17 P-estradiol, estrone:

6 testosterone, ethynyl estradiol

Isoflavones, l igans, coumestans, Phenolic

compounds