United Arab Emirates University
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Theses
Electronic Theses and Dissertations
6-2014
Identification and Quantification of Phthalates in
Polyethylene Terephthalate (PET) Water Bottles
Produced In the UAE.
Reem Mohamed Ismail Mohamed Ahmed
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Recommended Citation
Mohamed Ahmed, Reem Mohamed Ismail, "Identification and Quantification of Phthalates in Polyethylene Terephthalate (PET) Water Bottles Produced In the UAE." (2014).Theses. 240.
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College ofU � Engineering .:u.a.J 1 It d Arab EmlTates Umverslty a....u J.SU 1 LJ IJ lo � 1 a.st.o b
United Arab Emirate University College of Engineering
Department of Civil & En ironmental Engineering
l OE nFICA no AN D QUA TIFICA no OF PHTHALA TES IN POL YETHY LENE TERE PHTH A LATE ( P ET) WATER BOTTLES
PRODUCED 1 T H E UAE
Reem Mohamed I smail Mohamed Ahmed
This thesis is submitted in partial fulfi l l ment of the requirements for the Master of Science in Water Resources
Under the direction of Associate Professor Dr. Munjed Maraqa
D E L R A T I O N OF O RIG I AL WORK
L Reem M ohamed [smail M hamed hmed, the under igned, a graduate student at the United Arab EmIrates Uni\ ersity (UAEU) and the author of the the is titled " I dentl ficatlon and quanti ficatIOn of phthalates in P ET water bott les produced in the UAE". hereby solemnly declare that this thesis is an original work done and prepared by me under the guidance of Dr. Munjed M araqa in the Col lege or Engineering at U EU . Thi work has not been previoLlsly formed as the basis for the award of any degree, diploma or i m i lar title at this or any other un iversity. The material borrowed [rom other sources and included i n my thesi have been properly aek!10\\ ledged.
tuden!':; Signatu
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�P . ....,. " ... -.� .. -.-. . -. .. ....CopyrighL � 20 1 4 by Reem Mohamed Ismai l M ohamed A hmed A l l R ights Reserved
Approved by: Advi ory Committee:
1) dvi or: Dr. Munjed Maraqa Title: A ciate Professor
Department: Ci il and Environmental Engineering
In titution: United
�
ates Unj ersitySignature:. . . ... . . .. 7' ... Date: 5106/2014
2) Member: Dr. Mohamed Abdul Ruhman Meetani
Title: As ociate Profe sor
Department: Department of Chemistry
In titution: United Arab
.Ef
irates University Signature: .I��
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... Date: 5/0612014�
3) Member: Dr. a id B. SalehTitle: Assistant Professor
Department: Dept. of Civil, Architectural and Environmental Engineering.
Institution: University
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exas at AustinSignature: ...
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....
. Date: 5/06/2014The i Examination Committee:
1) Advi or: Dr. Munjed Maraqa Title: As ociate Profe or
Department: Ci il and Environmental Engineering
In titution: United
:�
ates Universityignature:. .
. . . .. .
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:
... Date: 5/06120142) Internal E aminer: Prof. Samir 1. Abu-Eishah Title: Profe or
Department: Chemical and Petroleum Engineering Institution: United Arab Emirates University
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Signature:.� ...
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ate: 5/06/2014(-'L
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/3 External Examiner: 't5r. Stuart Khan
Title: Associate Professor
Department: School of Civil & Environmental Engineering
Institution: University of Signature: ... .
Accepted by
Master' Program Director: Dr. Walid Al Shorbagy
Signa
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... Date: 5106/2014Dean of the
Prof.
A r 1 Die... Date: 5106/2014
A B T R A T
Thi the IS h ighl ights the criticallt; of phthalate ester (PEs). widely used in pIa -tic l1loldll1g and po es I I1g carcinogel1etic and tOXicological effects. The thesIs aim to asscss the prescnce and abundance of the e compound 1 11 polyethylene terephthalate (PET) bottled water produced in the UAE.
The the I te t for 6 types o f PEs (dimethyl phthalate (DM P), diethyl
phthalate (DFP), d i isobutyl phtha late ( O i B P), dibutyl phthalate (D B P ), butylbenzy l phthalate (B B P) and D i (2-ethylhexyl ) phthal ate (D E H P») i n widely u ed bottled water brands produced in the UAE. 1 26 bottled water samples were extracted by l iquid-l iquid extraction u ing petroleum ether, fol lowed by analysis of the target compounds u ing Gas Chromatography-M ass Spectrometry, with a l i m i t o f detection that range between 0.07 and 0 . 5 5 J..lg/L.
The study examined the impact of several parameters on leaching of P Es to bottled water contents i ncluding bottl e brand. e l va ted temperature sunl ight expo ure, storage time and bottle reu e. It al 0 underl ined the harmfulness of the
P Es concentration on human health, with detai l s about the commonly enforced regulations on these compound i n bottled water, both worldwide and i n the UAE. The only found P E was D i B P with an average concentration ranging between 0.6 and 2.6 J..lg/L. M oreover, none of the tcstcd parameters showed a c lear effect on l eaching o f P Es to ',: ater. Risk analysis was done based on the m ax i m u m detected D i B P ( 3 . 5 �lg/L) and the l i mits of quantification for all other PE . No substantial risk was observed . It is conc luded that UAE bottled water i safe for drinking from P E leac h i ng perspective . H owever it is recom mended that extra care shou ld be given to P ET bottle recycl ing; which was used for bottling products other than water as bottle source is suspected to be the reason behind any
found P Es i n PET bottled water all over the world, considering the fact that PEs arc not used in the synthe'ls of PET pia tic. I t is al 0 suggested to test water bottles during different steps of the bottl ing process, to identi fy the actual sources of PFs, whIch may not be the PET bottles. Finally, it is vital to do a comprehensive risk analysis to estimate the ri k of cumu lative exposure to P E s through di fferent channel..
K O'''LEDGElVIE T
Thanks to Dr. oh en Sherief who believed in me to do my M e in Water Resource' and upported me while he wa the dIrector of the program, although 1 came from a completely d i fferent field of omputer c ienee.
very spec ial tbanks to my gem (my mother) who accompanied me to all my long way tri p t o the university, and backed me extraordinari ly the whole way, em tionally and phy ieal ly in every way p s. ible. J also thank my family for their support and under tand ing whenever I had to spend long hours away from them to ach i ve thi goa 1 .
M any thank to M r . Yousef lebri l the Executive Vice President o f Power and Water P lanning Division at my work ( D E W A), who believed in my potentials and upported me extensively whenever [ needed to attend my classes and work
on my the is.
I a lso thank Dr. ehamuddin Galadari who gave me the push to reach thi step, when I \Va about to stop and drop everything completely, wh i l e he was the Provost of higher studies at the U A E University.
A very special tanks to my advisor Dr. Munjed M araqa, who supported me
at a l l t imes, understood the d i fficulties and pre sures I went through and kept me
on track. He provided me w ith knowledge and skills i n both l i fe and research theoretically and practical ly in many ways.
M any thanks to Dr. Mohammed M eetani for the great knowledge he provided me in i n trumental ana lysis and to Dr. Saleh Navid for acti ng as a co advisor of my thesis.
Thanks to Dr. H assan Abdul lah from the ollege of Food and gnculture at the U A E n i versily for hel ping me in the method development sample analy i and acqu i ring the needed data from the GC-M instrument. And thanks to Dr. A faf Kama l - Ed l l1 thc head of his department for her upport.
Thanks to Eng. alcm H egazy and Eng. Sami Ibrahi m from thc Collcgc of Engineering at the U A E Un iver i ty for help ing me whenever I needed.
[ also thank the exam ining comm ittce, the chair and all member of the Department of C i v i l and Environmcntal Engi necring at the U A E Univcrsity for a 'isting mc in my tudics and rcsearch.
D E D I T I O
I dedicate thIs thesis to my parent Fat Ima Subhi Abdul Salam and Mohamed Ismail l ohamed Ahmed Ahmed. [ wish that thi achievement completed thc dream that y u had � r me all tho c year ago when you cho e to g I ve me the ducation you could, and that you are proud of me.
T A B L E OF CO T E T T ITL[ PAG L . . . . .. ... . . ... . . .. .. ... . . . D I-CLARATIO OF O R I G I L WORK . . . .. . 1I OPYR f G H T P E . . . III S I G TURE P G E . . . IV B TR CT . . . V K \\'LE DG IE 'T . . . , D ED I CA T I O ' ... ... VII T B L E O F CO TE TS . . . ... VIII L J 'I O F TAB L - . . . ... . . ... ... . . ... . . . ... . . .. IX L l ST F Fl U R - . . . ... ... . . .. . . .. . X L l T OF ROt Y M . . . .. ... ... ... . . ... . . ... XI L I T O F Y M B L . . . ... . . ... . . ... . . . .. . . ... . . xu C H A PTER I : 1 TRODUCT 1 0 . . . .. . . 1 1 . 1 PROB LEM D E F I I T I O . . . .. .. . . 1 1 .2 O B J E T I E . . . .. . . 3 1 . 3 O P E OF WORK . . . 3 1 .4 A P P RO CH. . . .. . . ... . . .. . . 5 C H APTER 2 : L I T E RATUR E R E V I E W . . .. . . . . . . . . . . . . . . 6
2. 1 BOTTLED \ ATE R I NDUSTRy. . . 6
2.2 CO C E R J ABOUT BOTTLED WATER . . . . . . . . . 1 4 2.3 B OTTLED WAT E R R E G U LAT IONS . . . 20
2.4 PET BOTT L E . . . . . . . . . . . . . .. . . . . .. . . . . .. .. . . .. . . .. . . . . .. . . .. . . . 24
2 . 5 PE IN PET BOTTLED WATER . . . 27
2.6 H EALTH I MPACT OF PEs . . . 45
C H A PT E R 3 : M ETHODOLOGy .. . . 54
3 . 1 SE LECT I O N OF BOTTL E D WATER B R A ND S I N T H E UAE . . . 5 4 3.2 TARGET PEs . . . 5 4 3 . 3 S A M P L E P R E P A R A T I O N ( EXTRACT I O ) . . . .. . . . 5 4 3 .4 A A L Y I S M ET H O D . . . 5 5 3 . 5 CAL I B RAT I O N C U R V E S . . . .. . . 56
3 .6 PE RECOV E R Y TEST. . . 60
3.7 QUAL ITAT I VE TESTI G A D POTE TIAL LEACH ING O F PEs. 6 1 3 . 8 E X P E R IM E TAL S ETTING S . . . 62
C H A PT E R 4: I DE T I F I CAT I O N A ND QUANTI F I CA T I O N OF PE . . . 66
4 . 1 QUALITAT I V E TESTI NG RESU LTS . . . . . . . . . . . . . . . 66
4.2 POTE T I A L L E AC H I G OF PES . . . 66
4 . 3 E FF ECT OF STO RA G E T I M E . . . 68
4.4 EFFECT OF TEM P E RATUR E .. . . 7 2 4 . 5 E FFECT O F SUNL I G HT EXPOSURE . . . . . . 74
4.6 EFFECT OF BOTT L E R E U S E . . . 76
4 . 7 D ISCUSS I O OF R E S U LTS . . . 8 1 4 . 8 TOX I C ITY A ND R I S K A A L YS I S . . . 8 5 C H A PT E R 5: CON C L U S I O N A ND RECOM MEN DATIONS . . . 89
5 . 1 COl C LU S I O . . . 89
5 .2 RECOM M E DATIO S . . . 90
R E F E R E , CES . . . 92
APPE 'D ICES . . . . 9 8
TAB L E OF 0 T E TT
D I X A : BOTT L E D \V TER 01 TRlBUTIO H A ELS I N 9
E . . . . " . . . ... . . . ... ... . . . .
A P P E ID I X B : I 1 PO RTA '1' F A T ABO T P E D PLASTI 1 00 M TER r A L . . . . . A P P [ D I X . A L T B R T I O U R V E OF T H E T ESTE D P E . . . 1 0
A P P E 01 D . TEM PER T U R E P RO F I L E ( CTO B E R -DECE M B ER 1 1 3
20 1 3 ) I T H E U c ... . . APPE D I X E : BOTTL 0 WATE R M A R KET 0 BOTTLED J 1 5 W TER R EG U L A T I 0 1 1 T H E U A E . . .
T a b l e 1 :
T a b l e 2 :
T a b l e 3:
L I T OF TA B L E
E ncrgy and cm ironmental impact for o ft drinks containcr
verage dctccted PEs in d i fferent tudics reprcsented 1 11 �lg, L
amplc extraction, ample analy i techniques,
number f ample and L D of te ted P IJ1 different
tudie
1 9 47 48
Table 4: Retention time, c nfidencc Ie cl, L aD, LOQ and water 60
T a b l e 5 : T a b l e 6 : T a b l e 7 : T a b l e 8 : T a b l e A l T a b l e B l T a b l e B 2 : Table B3: T a b l e Cl: T a b l e C 2 : Table D l : T a b l e E l :
olub i l ity of the 6 lc ted P E
Frequcncy of testing for the inve tigated factors Average concentration of detected D i B P in diffc rent brand under the 3 exami ned factors reprcsented in
�g/L
Average c nc ntration of detected D i B P in different brand for bottle re-usc factor rcpre ented in pg/L Toxicity and carcinogenic effects of the tcsted phthalate
Bottled watcr distribution channels in the U A E Common industrial P E s and their chem ical structure Phy iochemical properties of P Es
P lastic classifications, reuse and recyc ling
Noi e signal at the tR of cach testcd phthalate for the 6 tested b lanks (3 d istil led watcr b lanks and 3 deionized water blanks)
The calculated value of each parametcr in equation ( 1 ) to (4)
Sunl ight duration, max and min daily temperature, rain fa l l in mm and global radiation for the period between 23 October and 30 December 20 1 3
Bottlcd watcr in the UAE, value by segment (AEDm), 2003-08
Ta b l e E 2 : Bottled water in the U A E , valuc forecast by segment
(AEDm), 2008- 1 3
T a b l e E3: Bottled water in the U A E volume by segment ( l iters,
m il lion), 2003-08
Table E 4 : Bottled water in the UAE, volume forecast by segmcnt
( l iters, m il l ion), 2008- 1 3
T a b l e E 5: Substances and parameters related to quality of bottled
drin king water
Tab l e E6: Chcmical substances natural l y occurring in ,vater
T a b l e E 7 : Chemicals used i n water treatment o r materials i n
contact with watcr
6 4-82 82 87 Appendix-A Appendix-B Appendix-B Appendix-B Appendix-C Appendix-C Appendix-D Appendix-E Appcndix-E Appendix-E Appendix-E Appcndix-E Appendix-E Appendix-E
Figure 1 : Figure 2 : Figure 3 : Figul'e 4: Figure 5 : Figure 6 : Figure 7 : Figure 8 : Figure 9: Figure 1 0 : Figure 1 1 : Figure 1 2 : Figure 1 3 : Figure 1 4 : Figure 1 5 : Figure 1 6 : Figure 1 7: Figure 1 8: Figure 1 9: Figure 20 : L I T OF F IGU R E
V orld bottled water con ul11ption in 20 1 1 , in mil l ion gallons 7 Bottled water consumption, in gal lons/capita/year for 2002 8 and 2007
Growth of bottled water market in the UAE between 2003 1 1 and 20 1 3
Bottled water brand market hare in 2008 1 1 Type of packaging lIsed for bottled water, in percentage, in 25
1 999
Generic chcmical ·tructure of phtha late c1iesters and 5 1
phthalate monocster metabolites.
elected mctabo l ites f DE BP in humans. 52
hromatogram o f standard 2 used in preparing the 5 8 calibration curve (prepared b y mi ing all tested PEs with concentration of 2 �lg/L for each P E in petroleum ether)
Chromatogram of standard 5 used in preparing the 59 calibration cur e (prepared by m ix i ng all tested PEs with concentration of 5 pg/L for each PE in petroleum ether)
hromatogram 0 f sp ike 1 (mix tu re of 1 00 pg/L of aeh of the 6 1 tested P E in d istil led water)
hromatogram of the creening test for one of the 3 bottles 67 o fMa ali brand, done to ch ck the initial contam ination w ith
P E s
Chromatogram of t h e screening test for o n e o f t h e 3 bottles 68 o f Evian brand, done to check the initial contamination w ith PEs
Chromatogram of the potential leaching of PEs test for one 69 o f the 3 bottles of Ma afi brand, done to identify the type and maximum amount of PEs that may l each from the wal l s of the bottles.
Chromatogram of the potential leaehing of P Es test for one 70 o f the 3 bottles of Al Ain brand, done to identify the type and maximum amount of PEs that may leach from the wal ls
o f the bottles.
Chromatogram of one of the 3 bottles of A l A in brand, 7 1 stored in a dark room at 20 °C w ithout sunlight exposure for 4 8 days.
Chromatogram of one of the 3 bottles of Al A in brand, 73 stored in the incubator at 40 °C without sun l ight exposure for 62 days .
ChTomatogram of a tested sample of one of the 3 bottles of 75 Aquafina brand stored under varying temperature with
sun l i ght exposure for 48 days .
Chromatogram of initial condition of water in one of the 3 78
tested bottles of Al Ain brand before bottle reuse.
Chromatogram of one of the 3 tested bottles o f M asafi brand, 79 after the first empty and refi l l with dist i l led water and storing
the sample in a dark room at 20 °C for 7 days.
Detected DiBP in the 3 tested brands (M asafi, A l A in and 82
Figlln� 21: Figul'c 2 2 : Figure 2 3 : Figure C l : Figure C2 : Figure C3 : Figure C4: Figul'e C5 : Figure C6: Figure E l : LI T OF FIGURE
qufina) a fter 'toring the bottl for 48 day under different storage conditi ons repre ented in Ilg/L.
Detected D i B P i n the 3 te ted brands ( M asafi, Al Ain and Aqufina) i n i tially and a fter storing the bottles in a dark room at 20 0 without unl ight exposure for different number of
day represented i n �lg/L.
3
Detected D I B P i n the 3 te ted brand ( M asafi, Al A i n and 83 Aqufina) initially and after st ring the bottles i nside the i ncubator at 40 II without unlight exp ure for different
number of days represented i n �lg/L.
Detected DiBP represented in �lg /L in the 3 tested brands 83 M a a fi , !\l in and q ufi na) initial ly and after storing the
bottle outdoor at varying temperature with sunl ight expo me for di fferent number of days,
DM P Calibration urve
D E P alibration Curve D i B P Calibration urve D B P Calibration C urve B B P Calibration urve D E H P Cal ibration Curve
B ottled water in the UAE category growth comparison, by value, 2003- 1 3 Append ix-C Appendix-C Append ix-C Appendix-C Append ix-C Appendix-C Appendi x -E
Figurc E 2 : Bottled water i n t h e U A E , category growth comparison, b y Appendix -E volume, 2003 - 1 3
Figurc E3: Bottled water i n the UAE, company share by volume ( %) Appendix-E 2007-08
Figure E4: B ottled water i n the UAE, distribution channels by volume Appendix-E
Acronym A'n B B P B O P B P D B P DCBP D D P D E ll D E l I P D E P D H P D i B P DlD P D i � P DlO P DMP D n B P D n H P D n O P D C DT D P D P D7 1 l P E CC E DCs E FS E Pn"I . EU FDA F S F SH G C G C-:\IS G SO H PLC H P\' I S IB\VA LD LLE Ko\\ L I T OF Ae R O Y 1 Meaning
rab Emirate Dirhams Butylbenzyl phthalate B ls(l-octyl) phthalate Boiling Point
hemieal b tracts Serv ice Dlbutyl phthalate
D icylohexyl phthal ate Didecyl phtha late
B i s(2-ethy lhexyl) adipatc Di(2-ethylhexyl ) Phthalate Dicthyl phthalate
Dihcxyl phthal ate D i i sobutyl phthalate Dii odecyl phtha late D i -i ol1onyl phthalate D i i ooctyl phthalate Di methyl phthalate Di-n-butyl phthalate D i-n-hexyl phthalate Di -n-oety l phthalate
D i fferential scan ni ng calorimetry Ditridecyl phthalate
D i undecyl phthalate
Diheptyl phthalate; H ptyl nonyl phthalate' Di nonyl phthalate; H eptyl u ndecyl phthalate; Nonyl undecyl phthalate
The European Consumer Centre Endocrine D isrupting Compounds European Food Safety Authority
E timation Program I nterface for W indows European Union
Food and Drugs Admini tration Full scan
Fol l icle stimulating honTIones Ga chromatography
Gas chromatography- mass spectrometry Gulf Standard ization Organization
H igh-performance liquid chromatography H igh production volume
I nternal standard
I nternational Bottled Water Assoc iation Liquid desorption
Liquid-l iquid extraction
Octanol-water partition coeffIc ient
cronym L O O OQ L O L LVI I B.lP 1\1 L tECPP l\l EllllP M E H P l\IE O H P M E P I P 1\1 �IST � R DC POM P DMS/DVB PEs PET PhA PVC R O SB E SI1\1 S M L SO DIS S PE S P:vIE TOI T D S T I C TOC A E US SA U S E PA \' VP WHO 610P LI T OF AeRO Ty I Meaning L l lnit of detection
Limit of quanti fication Limit of l i neanty
Large olume injection Monobenzyl phthalate
Maximum contami nant level
Mono(2-ethyl-5-carboxypentyl) phthalate Mono(2 -ethyl-5-hydroxybexyl) phthalate Mono(2-ethyl hexyl) phthalate
10110(2-ethyl-5-oxohexyl) phthal ate M onoethyl phthalate
Melting Point
Mass spectrometer
ational I nstitute of Standard and Technology Tatura l Resources Defense Counc i l
P I y (di methylsil oxane)
Poly (dimethyl ilo 'ane)/divinylbenzene Phthalate ester I phthalates
Polyethylene terephthalate
Phthalic acid Polyvinyl chloride
Relative standard deviation Stir bar sorptive extraction Selected ion monitoring Spec ific m i gration l evel olar water d i infection Solid-phase extraction
olid-phase m icro extraction Tolerable daily i ntake
Total d issol ved sol ids Total ion count
Total organic carbon
United A rab E m i rates United States
United States of A merica
Un ited S tates Environmental Protection Agency U ltraviolet
Vapor pressure
World Health Organization
I ,2-benzenedicarboxyl i c acid, m ixed Decyl, H exyl and Octyl d iesters
ymbol A T B\\ c DI ma\. Fe o oz G J H e IR k LOQ m :\ l eOH NaCl N O, pH R2 RID tR S Sm Sbl Sbl SO, vlv L I T O F Y 1 BO L Meaning
L i fetime averaging time; a uming 70 years x 365 days = 25550 Days
A vcragc body \velght; as lllned 70 kg oncentration of that particular signal
'hronic daily i ntake representing the maximum dai ly dose (mg kg, d)
MaX 1 ll1U111 concentration in the contam i nated waler (mg/L) L i m i t of detecti n (LOD)
arbon d ioxide
Expo me duration; assumed to be 350 day/year x30 years = 1 0500
Jays
Fraction contaminated; assumed to be 1 00% Fluid ounce
G iga joulc
H e l ium
Dai ly i ntake rate; a umed to be 2 L water/day for an adu l t
on tant repre enting a mUltiple o f the standard deviation usually =3
L im i t of quanti fication
S lope o f the cal ibration curve M ethanol
Sodium chloride Mono Titrogen Ox ides
The power of H ydrogen a calc to measure the acidity of a solution Coefficient of dete1111i nation of the best fit l i ne
Reference do e
Retention time
M easured s ignal
The lowest d i tingui hable signal M ean o f the b lank signals
Standard deviation of the blank signals Sulphur Ox ide
olume to volume ratio
H P T E R 1 : I TT R O D U T I ON
I . ] PRO BLE1\l O E FI N I T I O .
Good water qual Ity, and its avai lability in sufficient quantities, I \ ital for
human l Ife. H owever, i n 2002, 1 7°'0 of the gl bal popu lation ( I .e. 1 . 1 bill ion people) we reported t lac k access for suffic ient water supp ly, and many more had to consume m icrob iologica l l y contami nated water. Th is situation leads to a higb risk o f waterborn' disease such as dian-hea, cholera, typho id fever, hepatitis A and many other d isea es ( chmid et a I . , 2008). The World Health Organ ization ( W H O, 2004) reported 1 . 8 m i l l ion deaths on yearly basis because of d ian-hea, 90% o f which were children under the age of five primari l y i n developing countries. This i s equivalent to about 4500 chi ldren dying eaeh day.
Bottled water i ndustry started i n the beginning of the n ineteenth century, when the new gla s tecl1l1010gies made it affordab l e and practical to produce bottled water and d i stribute it among l arge population. I n the early twentieth century, a new perception of tap water took p lace with the arrival of ch lorination in municipa l drin king water supplies; which made pub l ic water consistently healthy and safe to drink. This caused bottled water to go out o f tyle and need. But i n 1 977, health concerns assoc iated with pol lution and poor qual ity tap water caused bottled \ovater to come back again ( H a l l , 20 1 0).
H owever, general pub l i c perception that bottl ed water is safer or health ier than tap water may not be true. The U n i ted States Natural Resources Dcfcn e Counc i l study ( RDC, 1 999) of the bottled water industry-bacterial and chemical contammation analysis-included independent laboratory testing of more than 1 ,000 bottles of 1 03 types and concl uded "about one third of the bottled
waters they tested contained 'ilgni ficant contammation ( i.e., le\'els of chemical or bactenal contami nants c ceedtng those allowed under a tate or industry tandard or guideli ne) in at least one test". They [1.uther found "about one fifth of tbc \ atef contained synthetic orgal1le chemical , uch as industrial chemicals ( i .e., toluene or xyl ne) or chemicals used in manufacturing plastic (i.e. phthalate esters (PEs), adipatc, or tyrene)" ( 1 1 a l l , 20 1 0).
P lastic pr ducts arc u cd i n everyday activities In the modern society
(\ HO, 1 997). P lastic is considered the most lIsed packaging material by market value. pproxi mately, 70°'0 of the overal l consumer packaging consumption is u oed for food and be erage packaging i ndustry ( World Packaging Organization, 200 ). i nce the beginning of p lastic production i n 1 862, the technology of i ts production has signi ficantly changed. Currently, various agents are added in pia tic material processing to i mprove it properties, such as softeners, p lasticizers, fi l ling , stab i l izers, and pigments. For several decades now, phthalic acid esters know n as phthalates have been the mo t widely used p lasticizers, w ith d i (2-ethyl hexyl) phthalate (DEE P ) accounting for 50% of thi s uti lization ( Bosnir et a l . , 2007). The production o f phthal ates i n the world has grown to 3 .5 m i l l ion tons per year (Bornehag et a l . , 2004). The proportion of phthalates in a plastic material may account for almost 45% o f its mass, depending on the type and purpose of the product (WHO, 1 997).
Despi te the w i de spread use of p lastic material for food and beverage
packaging, the role of plastic as a source of contami nants has received l ittle
attention (Grob et a l . , 2006). A few stud ies have demonstrated signi ficant leaching
o f phthalates (espec ial ly those identi fied as endoc rine d isrupting compounds
( E DCs), primari l y used as plasticizers) from packaging material l..lch as
polyethylene terephthalate (PET) bottle into food and beverages. These studie demonstrated that leaching of ol11e ED s arc not only considerable, but arc also h ighly influenced by ambient condition (such as temperature) (Sax, 20 10).
E OCs can m i m i c natural honnones i n the end crine ystems of animal s, and thus adversely i mpact ceo ystcms and human health by disruptll1g growth, development, and reproduction (J eph et aI., 20 1 1 ). Such find i ngs raise a concern regard i ng the potential re lea e of E DCs from pl astic packaging materia l , a n d i f needed de\·elop a pas i b l e solution t o contro l t h e release of these tox i c u b tance from plastic packaging in the food i ndu try t o ensure safety o f PET bottl e usage.
1 .2 O BJECTI V E S
The main obj ectives of the thesis are:
A. To identify the key leached PEs from PET water bottles produced in the United Arab Emirates (UAE).
B . To quantify the level of the identified PEs under simulated scenarios that m i m ic conditions encountered in the U A E . Varying parameters wi l l include bottl e water brand, storage time, storage temperature, sunlight exposure and bottle reuse.
1 .3 SCO PE O F WORK
There arc 2 1 known commercial PEs, out of which 6 PEs ( i .e. di methyl
phthalate (DMP), d iethyl phthalate ( DEP), O E H P , disobutyl phthalate ( D i B P), di n-butyl phthalate ( D B P) and butylbenzy l phthalate ( B B P) ) arc reported in l iterature to be present at detectable level s in bott led water produced in several countries. These P Es are targeted in the current study for identification and quanti fication in bottled water produced in the UAE.
n initial screening was done for 6 PET bottled water brands of Ize 500 ml commerc ial ized in the UA E, to check the initial state of watcr aftcr being purchased . Out of thc'c, threc major brands wcre cho cn for te ting the effect of d i fferent factors. The selectIon strategy of the targeted brand was based on company's producti n rate. Eighteen bottles (3 from cach brand) were used 111 the creel1ll1g process. c1d itlonally 18 empty bott les (3 from each brand) wcre analY7cd, to te t the maxi mum PEs concentration that may leach into bOltled water content. As the study i. targeting PET t i l l bottled water ( i .e. non-ilavored and non-carbonated bottled water), no glass, PE bottles, flavored or carbonated bottlcd water were tested.
ampl ing proces was repeated 4 t i mcs ( i . e . after 1 2, 24, 48 and 62 days period of time) in addition to the initial screcning process, to tcst the effect o f storage, temperature a n d exposure t o sun l ight o n l each i ng of phthalates into bottled water. The effect of bott le reuse was tested twice ( i .e. after the first and second reuse). Three bottles from each brand were used every time the samples are extracted . Based on this sampling procedure, 3 6 samples were used for testing the e ffect of each investjgated factor, except for bottle reuse where on ly 18 samples were tested.
To elucidate the e ffect of temperature; bottl es were stored at both 20°C (accounting for the best temperature storage conditions) and 40 °c (accounti ng for a severe storage conditions from a temperature point-of-view). Moreover, to exam ine the infl uence of exposure to sunl ight; some samples were stored i ndoor and other were stored outdoor for the same periods of time ( i . e . 1 2, 24,48 and 62 days). In the i nvestigation of bottled water reuse, an initial analysis for water contai ned in those bottles was done, then the bottles were emptied and refi lled one
time w ith distil led water and stored i n a dark room under 20 uC temperature for 7 days, and the another lime with deion ized water and stored under the ame condItion for another 7 day (to c reate the maxi mum gradient possible for the concentration of PEs between the \vater and its container), to test the consequence of stonng \\ ater [or the second and third time in the same container. 0 bott l es
were analyzed ncar the expiry date because bott led water consumption in the UAE i too high, causing the maxi mum age of the locally produced bottled water in the market to be 2 months only.
Thi process is repeated twice to cheek the effect of bottled water reuse twice before being disposed . Furthermore, deionized water and disti l led water were both tcsted to check for any initial contami nation with PEs.
1 .4 A P P RO A C H
T h i s study invo lve the fol lowing tasks:
Task 1 . De\"cloping a method for the analysis of PEs in bottled water.
Task 2 . I denti fication and quantification of the predom inant PE relcased from PET bottles produced i n the UAE.
Task 3 . Systematic studies of the predominant PEs release as a function of brand,
storage time, temperature, sunl ight exposure and bottle reuse.
H PT E R 2 : L I T E RA T R E R E V I E \V
2 . ] B OTTLE D W T , R I '0 T R Y
The already stre ed global water re ourees have been put under amplified pre sure due to population growth, increa 'ed standards of l iv ing in developing countrI es, and c l i mate changc, which lead to prompted ehanges in peoples' hab its of potable water con llmption (\ ait, 2008 ). In spite of the avai l abil ity of cheap good quality tap water in many indu trial countrie , bottled water consumption tremendOll Iy i ncreased in thc past 3 0 years at an annual growth rate of 7% worldwide. fn 1 976, for e 'ample, the average bottl ed water consumption in US was 5.7 gallonlcapita/year, compared to 9.2 gal lon/capita/year i n 1 999 ( FeITier, 200 1 ). Another tudy (Olson, 1 999) showed that 54% o r Americans drink bottled
water.
In the year 2000, the world's bottled water market reached an annual volume of 22.4 b i l l ion gal lons, accounting for an average consumption of 4 gal l ons/capita/year (Danone, 2000). Westem European countries used to consume half of the world bottlcd water, with an average of 22.4 gal lons/capi ta/year. Within Europe, I talians score the highest consumption with an average of 28 gal l on s/capita year (Sollbcrger, 1 994 ). Statistic shows that 59% of bottled water drunk worldwide is puri fied, whi l e the remaining is springs or m i neral water ( Belot 2000). Figu re I shows the distribution of the worl d ' s bottled watcr consumption in 20 1 1 ( Rodwan, 20 1 2).
A lthough in the 1 9th century major bottled water consumption was located in Europe and orth America, the 20th century prompts of promisi ng growth of bottled water i ndustry in A ia and P ac i fic, wh ich witnessed a yearly growth of
1 5% betwcen 1 999 and 200 ) (Ferrier, 200 ) ) . Fra nce, 2,29 1 .0 Germa ny, 2,954. 2 '" I taly, 3,034.7 I n dones ia, 3,760.6
r
spain, 1 ,5 1 4.6Figure l : World bottled watcr consumption in 20 1 I , in m i l l ion gal lons ( Rodwan,
20 1 2)
I n I ndia for i nstance thc tum over o f morc than 1 00 bottled water companies i US$ 70 m i l l ion. growing at an average yearly rate of 1 5% ( Raphel.
1 998). I t has a lso been e timated that the global average consumption of bottled water i ncreased by more than 40% between 2000 and 2005 ( Worldwatch I nstitute, 2007).
I n arid regions where non conventional water resources arc uti l ized ( i.c. water desa l i nation). i ncreases in bottled watcr consumption were more noticeab le, a doubl ing bottled water consumption was reported in the Middle East between 2003 and 2008 ( Wait. 2008 ). According to the Beverage Marketing Corporation
(2008 ) for annual bottl ed watcr consumption i n 2007, UAE was leading the world
in thc annual per capita bottled water consumption of 68.6 gallons, compared to
54. 1 gal lons in Mex ico, 5 3 .3 gal lons in I taly, 3 5 . 8 gal lons in France, 29.3 gal lons i n the Un ited States, 24. 1 gal lons in nearby Saudi Arabia, and a global average of
7.6 gal lons. Figure 2 hows the detai led bottled water consumption rate for twenty countries all over the \ orId i n 2002 and 2007.
80 70 � 60 C. '" u so C 02002 � 0. 40 E :J 30 '" c 0 U 20 � :J 10 c c � 0 w 8 � E ., '" £ 0:: .. � '0 ..
�
.� '" " ., '0 .. ;; ..: " ::I U 0:: " 0 .. 0:: c: :0 ... .D ::I 0:: � 0> X 0:: � 0:: .. " a. :::> ., m t:! a. " 0> .. ::I 0 .. .., ::I '" in 0:: 1; ::I .:t '" t: :l! '0 u. .0 ::I ., a. 0 '" <> " !j ..: ., U .s= 0III (!) ...J " I iii '" 'i5 t- a.
.. 'j .<:; � c '" u :::> ., '" " u Country
Figure 2 : Bottled water consumption, i n gallons/capita/year for 2002 and 2007 (Beverage M arketing Corporation, 2008)
A lthough all bottled water brands available i n retai l shops look the same,
the contained product is d iverse i n its origin and chemical composition. There are
three major types of bottled water the first type is natural mi neral water originating from underground aqu i fers and emerges from spring through natural pores. It usu a l ly contains constant level of m i nerals and trace elements. General ly,
it undergoes restricted treatment procedure that does not alter its chemical
characteristic , l i ke separation o f unstable c lements and undesirable constituents, and removal of free carbon d ioxide. The second type is spring water, which is underground water that is natura l ly protected from pollution, healthy for human use without additional treatment except for the removal of trapped gases through
aeration ( Fen-ier, 200 I ).
European countries distinguish between natural mineral water and spri ng water as the l atter should strictly fo l low drinking water standards, "does not need to have a constant mineral composition" and is cheaper. W hereas in US, spring
watcr is underground watcr col lected at springs. or through bore hole taping to thc samc formallon originating the pring watcr. \\ herc thc cxtracted watcr houl d havc t h e same phy i c a l and chemical propcrtics of watcr flowing natura l ly before trcatmcnt. Thc third type is pUrI fied \\ atcr, which originates from the sea. lakes. rivcrs and underground springs. and undergoc fu l l trcatment process. PUri fied water i simi l ar Lo municipal watcr in pricc and distribution method with minor d i ffcrcnces i n the chcm ical composition ( Ferricr, 200 I ).
I n add ition to tbc three main typcs mcntioned above, the I ntcrnational Bottled Water A ,ociation ( I B W A ) considers four add itional bottled water types, which arc : artc ian well water that is tappi ng from a confi ned aquifer, where water reachcs the surface at one side of the aqu i fer at a point above the watcr table, wcll water which comes from dri l led borcholcs reaching tbc water table i n the aquifer, sparkl i ng water which is treated water that contai ns thc same amount of carbon d ioxide before and after treatment, and drinking watcr which is flavorcd water that is free from sweeteners or chem ical addi tivcs except the addcd natural es ences or extracts. Flavored water shou ld be calorie-free and the amount o f added fl avor should not exceed 1 % of the bottled water weight, it may also contai n very low amount of sodium ( I BWA, 2000).
Bottled water industry in the UAE accounts for 22.8% share of the total soft drinks market. It consists of four main typcs; sti l l unflavored, sti l l fla ored,
pm'kl ing unflavored and sparkl ing fl avored. Sti l l unflavored watcr i ncludes m i ncral watcr, spring water and treated tap watcr packed in contai ners below fi ve l i ters. This type l eads the market by embodying 94.3% of bottl ed water produccd in the country. Spark l i ng flavored and sparkl ing unflavored water includc mineral water, spring water and treatcd tap watcr that arc natura l ly or artificially
carbonated with or without added fruit fla\'oring, and packed in containers below five liters. They account for 1 . 1 % and 4 .4% market share. respectively. t i l l Oavored water h a the least markel hare o f O. J % ( Datamonitor, 20 1 1 ) .
Bottled watcr market in the U A E had grown from 2003 to 2008 by 1 4%, accounting for AED 3 1 9. mil lion. I n 2003, bottled water market value was E D
46.9 m i l l IOn with a total volume o f 429.2 m i l l ion l iters whi l e i n 2008 i t had markedly increa ed to i\ E D 666.7 m i l l ion, representing a total volume of 769 m i l l ion liters. The forecasted market value i expected to be AED 1 ,046.6 million by the end o f 20 1 3 , representing a total olume of 1 , 1 55.6 m i llion liters. The total growth between 2008 and 20 1 3 i s expected to be 9 A%; which accounts for money
increase of A E D 79.9 m i l l ion of sales. F igu re 3 represents the growth of bottled
water market i n the U AE between 2003 and 20 1 3 (Datamonitor, 20 1 1 ).
I n the UAE, there are 6 principal companies produc ing bottled water. Each of which holds the l icense of a particular bottled water brand. M asafi Mineral Water Company (produces M asafi minera l water), E m i rates Foodstuff and M ineral Water Company (produces Al A i n m ineral water), Groupe Danone (produces Evian bottled water), Pepsico I nc (produces Aquafina bottled water), ational Food P roduct Company (produces Oa is bottled water), and Arwa M i neral Water Company (produces Arwa bottled water). Figu re 4 summarizes the leading m ineral water brands in the U A E and the market share of each brand i n 2008. Other smaller companies hold the l icense o f the remaining bottled water brands and have 5.7% market share. It should be noted tbat a simi lar trend as that sho\'.'n i n F i g u re 4 was observed for reported data of 2007 ( Datamon i tor, 20 1 1 ) .
1155.6
1 200
1000
800
.. Volume (liters. million) .,
� '" 600 Market value (mAEO)
> 400 200 0 2003 2008 2013 Year
F i a u rc 3 : Growth o f bottled \valer market i n the UAE between 2003 and 20 1 3 ( Datal1lonitor, 20 1 I )
Aquafina, 6.5% Oasis, 6.1% 1
F i g u re 4 : Bottled water brands market share i n 2008 ( Datamonitor, 20 1 1 )
Bottled water market in the U A E encompasses several channels. Table A l l ists a l l bottled water channels i n the U A E and their description. Among tho e channels. superIl1 arkets and hypermarkets distributed the largest volume of bottled water of 4 3 8 . 3 m i l l ion l iters in 2008, fol l owed by retai lers and convenience store
for which the reported d istributed volumes in 2008 were 1 5 6.9 and 98 m i l li on l i ters. respectively (Datamon itor 20 1 1 ) . For additional deta i l s about bott led water market in the U A E please refer to Appendix E.
The worldwide ever-growing bottled water industry can be attributed to many reason . Tap water odor and bad ta te come fi rst in the l ist. About hal f of
compared to 7% In U (01 on, 1 999). Tap water taste yanes according to location, treatment technique and chlorine concentrati n. Following this comes health concerns and people's belief of tap water a being unsafe. Thi belief is main l y due to previous bacterial contaminatIOn, seasonal hortage of tap water, fear of fecal contammal Ion, t xic substance. r h igb nitrate levels in agriculture area and water runnll1g in old distribution pipelines ( Ferrier, 200 I ). " I n 1 996 al most 1 0% of community tap water systcms serving 1 4% of US population vio lated fedcral United tates Environmental Protcction Agency (US EPA) tap water treatment or contami nant tandards in 1 999" (Olson, 1 999).
Peop le a lso drink bott led water think ing it ha additional benefits for their hcalth. This idea is rootcd to an old European tradition when people used to visit the pa and drink m i neral water to treat d i fferent disease. Nowadays, the idea is sti l l there with a more fa h ionablc look, as people started buying bottled water as a response to ad er1ising that says bottled water is good for wel l -being, slimming, energy and fitness. Moreover. many consumers believe that m ineral bottled water originated from springs wells or rivers has some sort of magical treating power
( Fenier, 200 1 ).
The fact that bottled water is healthier than other beverages l ike soda,
alcohol and beverages containing artificial swecteners or coloring also helped
i ncreasing the market of bottled water. Bottled water is being chosen as healthy
alternative assisting weight loss for most females and adults. H owever, this idea is
not true. Bottled water may contain sma l l amounts of minerals such as calc ium,
m agnesium and fluoride, but those same amounts can be found i n tap water. and
unless tap water is contaminated by an external sourcc, both tap water and bottled
water have the sam e natural val ue ( Fenier, 200 1 ) .
Change of l I fe tyle played an i mportant role in l I1creasi ng bottled water market. lncrcasing urbanization lead to dcc l t n l l1g tap water qua l ity and the fa t solution \vas switching to the safer bottled water. FUrlheD110re, as natural mllleral water docs not undergo any treatment and has no additives. people who arc adopting the concept of cat ing rmv food arc considering it as green healthy product. I ncrea i ng standards of l iving, extensive usc of car , the wide spread markets e U mg bottled water and the l ight weight plastic bottles encouraged peopJc to g [or this expensive option, where they can drive to any market easily and buy boxes of water to their homes. Changes i n working habits and shifting from agriculture j obs to offices grow a new culture of having the easy access bottl e on the desk beside the worker s phone and computer. I n addition to all of tho e factor come bottled water advertising, which had a great hand i n tremendously enlarging the bottled water market ( Ferrier, 200 1 ).
A lthough the production cost of bottled water is very low ( less than AED 0.04 for one Evian bottle), i ts price is tremendously high compared to tap water (about 500 to 1 000 times higher). The excessive money people pay mainly goes for bott l i ng, packaging, transport, marketing and reta i lers p rofit (Ferrier, 200 1 ). According to O l son ( 1 999), one-third of the bottl e price is a profit.
Wait (2008) conducted a survey to examine people s perception of bottled versus tap water for drinking purposes in the DAE, in an attempt to explain this social phenomenon . The surveyed people werc asked "when you ha e a choice, which do you prefer to drink?". About 87 .2% of the respondents selected bottled water and the rest se l ected tap water. Those pre ferring bottled water were asked to indicate the reasons why it was their preferred choice, and were given the option to select more than one reason. About 76.4% of the responses indicated that
"bottled water is more healthy" , 5 8% indIcated " bottled water tastes better", 2 5 . 5 % ind icated "bottled water is more portable and com'enient than tap water", 15% ind icated "I pre fer the temperature of bottled water more than that of tap
water", 1 1 .50 0 indIcated 'tap water is not a ailable when I want to drink", 6. 1 o,� indicated "1 prefer bottled watcr becau e of ocial pre sure", and 23.20/0 indIcated other rca on . In a que lion about the prefen-ed type of bottled water, 57% of the re pondents answered "bottled water that comes from underground (i .e. wel ls, springs. etc. )", 20.8% said that it doesn't matter, 1 9 .7% selected "bottled water that comes from a fre hwater surface OUIce, such a a lake, river, or stream", and only 2 . 5 °'0 aid "bottled water that comes from desalination of sea water".
According to Wait (2008 ), the main two reasons of peoples' preference of bottled water to tap water i n the UAE arc related to waler qual ity issues : the I nsight that bottled water possess h igher qual ity than tap water, and the preferred taste of bottled water a groundwater and desa l inated water are purified and re m ineral i zed much more than tap water. 'Wh i l e respondents extremely favored bottled water ( 8 7 . 2%) to tap water ( 1 2 . 8%), 57.3% did not have preferab le brand of bottled water, 44. 1 % prefe rred domestic bottled water, 40.8% had no preference when choosing between dome tic and i mported bottled water, and
1 5 . 1 % indicated a preference for imported bottled water.
2 . 2 CONC E RNS B O U T BOTT L E D WAT E R
A l though demand for tap water i n the UAE 1 S constantly increas ing,
people habitually avoid using it for drinking and someti mes cooki ng purposes, as pub l ic perception about i ts qual ity is generally low. It is uncommon to fi nd pub l ic drinking fountains or to usc tap water i n restaurants for drinking purposes. People do not only usc bottled water whenever they are outside their homes, but they also
uti l I ze at-homc bottled water del Ivcry most of thc time (Wait, 200 ).
H owc\er, thc I l1sighl of the supenor healthful ness of bottled water to tap water ha been questioned in the US for everal years. In a tudy related to limit o f bacteria. inorgamc eontamll1ams, and carcinogenic chemicals uch a phtha lates. it was found that one-third of bottled water samples fai led to meet the gu idelincs (01 on, 1 999). W h i le the U E P A cnforces strict regulations on tap water, thc Food and Drug dministration is regu lating bottled water with more l en icnt et o f regu lations. There i a lso evidencc that bottled water in the developing world i not as healthy as ometi mes proclaimed. For example, an analysi of 1 7 different brands of bottled water in I ndia found concentrations of essential m ineral u h as magnesium, potas ium, and calcium to be lower than the W H O l i mits, and that the concentration of lead was exceeded in 7 of the 1 7
brands tested ( Wait 2008) .
2.2. 1 Bottled }voter quolity
Extcnsive research ha been conducted to study the suitab i l ity of PET materials for food packaging. I n this regards, migration of m i nor constituents from packaging material i nto bottle contents that may possess tox icological e ffect drew a large concern ( Farhoodi et a ! . , 2008). Some studi es (Nerin et a l . 200 3 ) have been done t o check thc type and concentration o f compounds resul ting from post-consumer P ET recyc l i ng. Other studies (Widen et aI., 2004) i nvestigated the effect of the recyc l ing process on purposely-contaminated P ET
material. to dete1111 ine the potential m igration of contam i nants from containers to
the packed food.
I nteraction between packaging material and contained product may cause h igh amount of migration into bottle contents which may lead to changes in the
packaging tructure (farh odl et a!., 2008). DIfferentIal scanning calorimetry wa used by W iden et a ! . (2004) to examine the effect of dIfferent simulants on the m igration of model contaminants. Pennarun et a!. (2004) tested the effect of food s l l1l ulant' on the d lffu ion coefficient of migrant molecules from recycled PET bottles.
P E are indu, trial chemicals with high persistence and great m igration potential from plastic containers, which possess endocrine disrupting properties and exhibit the highe t aquatic toxicity . They have been articu lated by the European Commission in "the priority l ist of substances for further eva luation of theIr role in endocrine disruption " . They are commonly used as p last icizers i n pIa tic bottles i ndustry (G lobal producti.on of phthalates is over 4 mil l ion ton/year). They also possess estrogenic effects that may lead to odor/taste problem and cau c the growth of m i crobial flora . Despi te their d isrupting effects, there is no systematic approach to control drinking \;vater organic contents ( i nc luding PEs) and monitor their ources. Lack of infonnation about EDCs ( i nc luding PEs) is due to d i fficul ties i n analyzing them in trace quantities (Ca ajuana and Lacorte, 2003 ) .
Most of the stud ies about leaching of P E s from containers t o bottle contents reported h igh amounts o f PEs i n ease of low p H contents, and only trace amounts in case of water. Nevertheless, b ioassays of incubated cu ltures in water with near-neutral pH for Ie s than 2 months showed signi ficant estrogenic effects in most of the tested samples. These results draw the attention towards other E DCs, \vhich may reside in bottled water contents . Antimony ch loride i one of the compounds with potential estrogenic effects. It is extensively used catalyst in the polycondensation of PET (Sax, 20 1 0).
I n a survey conducted by the U E PA i n 1 986 on 2 5 bottlers, it wa found that none of the bottlers had ful l analy is of their water and 8% of the tested water was contam inated with bacteria. Moreover, anitary provisions \"here not strictly [ol lo\\cd, as bottle' u cd to aITive to the bottl ing plant uncapped and filled with \ ater without being rin ed properly. On the other hand, the JRDC proclaimed that bott led \\ater is safe to drink, however many incidents like bacterial and chemical contam i nation, algae, excessIve chlorine and other sorts of contamination were faced by bott ler and they had to re olve them avoiding any pub l ic announcements ( Ferrier, 200 I ).
I n 1 990. the withdrawal of 280 m i l l ion bottles from 750,000 sale points worldwide. due to benzene concentration exceeding US tandards (8 to 1 7 �lg/L i n tead of 5 �lg/L) co t Perrier around 1 3 3 m i l l ion . Another survey in 1 997 in U S howed that most c a n tllners don ' t get enough i n folmation about t h e contents of the bottled water they are drinking. In most cases it is not accessible or not enough, or even in some cases written with unreadable font on bottles' labe ls
( Ferrier, 200 1 ).
2.2.2 Bottled water environmental impacts
As p lastic container are being progressively used in a l l human field , the
total solid waste generated by plastic is growing by I % every year, causing a great problem. due to its massive volumes and non-biodegradabi l ity (WHO, 1 997). H owever, recent studies show that sol i d waste generated from p lastic undergoes degradation in slow rates when exposed to weather conditions l ike sun, rain and now, causing the release of PEs into the surrounding environment, which may
then leach to the underground water i ntended for human use (WHO, 1 997). On the other hand, improper plastic burning may release other toxic compounds I ike
dioX l I1s and furans ( 1:3osnl r et a t . . 2007).
A recent article published i n the Gul f ews by Asger (20 I 0), revealed erious fact about bottled water torage in unhygienic places before being consumed. ome bottled water compan ies perform a deal with bui ldings' watchmcn, i n which they sel l them multiple fivc-gallon water bottle on daily bas Is for AED 5 instead of AED 7. Watchmen then ell these bottle to building residents [or A E D 6 or 6 . 5 . uch dea ls lack any pecification for storing bottled water i n environmentally clean places before distribution, leaving watchmen free to tore the'c bottles under the un for several weeks or even i n garbage rool11s.
A garbage attracts fl ies canymg everal disea es l ike hepatitis A, ga troenteritis, and sal mone l losis (typhoid fever), human consuming bottled water tared in garbage rooms could be infected by one or more of those fl y-borne d isea es. M oreover, exposure of bottl e to sun l ight especially during summer (when temperature in the U A E reaches 40 °C or above) could infl uence the quality of water. As a result, strict regul ations need to be put in p lace, prohibiting buildi ngs' watchmen, and in some cases freelance salesmen from storing bottled water in un-hygienic conditions (Asger, 20 ( 0).
I n addition to bottled water potential effect on human health through i ngestion, its manufacturing, transporting as well as recycl ing impl ies energy consumption and pol lu tants emlSSlon into sunounding environment. Manufacturi ng of p lastic bottles for example may rel ease phthalates and other c hemicals into water, air and other environmental systems ( Ferrier, 200 I ).
The three main environmental i mpacts consi dered whi l e choosing between p l astic, glass and aluminum packaging material are energy req uirement,
atmospheric emissions and solid waste produced. Table 1 summarizes the effect
of recyclmg different bottl ing materia l o n the em ironment. A the tab le i m p l i e ,
the rccycl i ng process J not the best environmental friendly option, due to the high-energy con umption and fue l c mbustJOI1 required by this proces . A bettcr altcrnati\ c can be wash ing and refi l l ing the refi l lable bottles. However, i f transportation is required, w h i c b mean more fucl will bc con umed b y vehicles
causing higher emi sion levels 0 r NOx, SO, and O2, this option can no longer be considered a fer for the environment ( Ferrier, 200 1 ) .
Table 1 : Energy and environmental i mpact for oft drinks containers (Ferrier.
200 1 )
C ontainer type Recycling rate
0% 50% 1 00%
Energy reqUired (GJ per 1000 litres)
PET (64 fl oz bottles)29 5.9 5.0 4 . 1
Aluminium (12 fl o z cans) 1 3.9 9.2 4.4
Glass (16 fl oz bottles) 1 3.7 9.8 5.8
Atmospheric emissions (kg per 1000 litres)
PET (64 fl oz bottles) 7.4 6.4 5.4
Aluminium (12 ft oz cans) 1 6.4 1 1 .0 5.8
Glass (16 ft oz bottles) 26. 1 1 7. 5 8.8
Solid waste (kg per 1000 Ii/res)
PET (64 fi oz bottles) 6 1 .6 42.2 227
Aluminium (12 fl oz cans) 232.6 1 28.2 23.8
Glass (16 ft oz bottles) 840.0 465.7 9 1 . 5
Recycl i ng process should only be considered i f there is enough public awareness, avai labl e infrastructure and arranged col lection po ints, whicb may not be avai lab le in deve loping countries where bottl es are usually disposed, burnt or reu ed under unhygienic conditions. In addition to the actua l containers, water bottle arc usual l y sold in packs of 6 bottles wrapped \\'ith p lastic, produc i ng
additional p lastic waste ( Ferrier, 200 1 ) .
world via d i fferent tran portation routes, ha a negative impact on the en\ ironment, which can be l i mi ted by cho ing t trade for bottled water locally. Tran porting bottled water in bulk contai ner under triet hygienic conditions can al 0 help restrict lhi negative effect. Furthermore, international companies can i nvest i n the l ocal market by u i ng their brand ' labels on bottled water produced at local fac i l ities (Ferrier, 200 1 ) .
2 .3 BOTT L E D WAT E R R EG U LA T I O S
Regu lators i n ome cOLintrie require bottled water manufacturers to mention deta i led information about water origin and its composi tion on bottles' labels. The E uropean Union ( E U ) for example, asserts water name, source, certain treatments used and analytical composition including the constituents' characteristics to be written on the bottle label . E U forbi ds any type of health trading l ike prevention or cure of human i l l ness to be stated on bottles' labels. I t also bans dupl icated l abel s fro m being u sed for more than one source of bottled water ( Ferrier, 200 1 ) .
On the other hand, i n the U nited States many di fferent label s can be used for bottled water coming from the same source. I t is al a possible to find water coming from several sources during d i fferent t imes of the year, or sold in di s i m i lar locations, ha ing the same brand name (Olson, 1 999), which hardens the identification of the product.
M any P Es have been included by regulator ( l ike EU drink ing water regulations) i n the l ist of priority substances to be evaluated (European Union, 2006). But though the Committee on the Environment Public H aith and Food Safety proposed D B P to be i nc luded in this priority l ist in the Water Framework D i rective 2000/60/EC, it is not cUlTently considered in EU drinking water regulations (Comm ittee on the Environment, Public H ealth and Food Safety.
European Union, 2007). The legal water act in roatla regulated the total amount of phthalates in plastic material used for any purpose, any period of time and by any L1ser age, to be 35% (Page and LacroIx, 1 992).
A spring water cannot be treated, b ttlcd water companies took initiatives to protect sources of theIr spri ng water, but thIs included particular catchment area. leaving other \1\ ater sources at potential risk. Evian have bcen protecti ng
their spring' catchment area for the past 200 years by prohibiting any
onstruction activities. illtell lve agricultu re or cattlc brecding. Evian pays the fanners the d i fference i n co t between chemical ferti l i zers and green manure, as a further step to protect their springs from chemical contamination ( Fenier, 200 1 ) .
A l though tap water is aimed for daily human consumption, where natural
m i neral water is mainly used for drinking, the control measurc set by drinking
water directive on tap water i n U S A (62 parameters) is firmer than measures
enforced by natural mineral watcr d irectivc on bottled water (26 parameters). The
ame situation is repeated in the United State , as they consider tap water as uti l ity water, which regulated by the U S EPA, while bottled water is considered type of food product, which is regu lated by the more len ient Food and Drugs
Administration (FDA) (Ferrier, 200 I ).
Bottled water regulation does not ban fecal col i form , and is tested less frequently for chemical and bio logical contami nation than tap water. In addition about 60-70% o f carbonated and disinfected bottled water, and bottled watcr sold within the same state of its production are exempted from regu lation (Ferrier, 200 1 ). The US E P A has estab l ished M C L of D E H P in drinking water of 6 �lg/L,
which is fol l owed by many states in U S except i n California, where the MCL of D E H P in drinking watcr is 4 �lg/L (Mac ler, 2009). I n addition to this, rile U S EPA
requIre screcnmg proce of PEs in drinking watcr at concentration abO\"e 0.6 �lg/L (US EPA, 1 99 1 ).
I n I ndia, no bottled water testing routines, contai ners hygiene requirements or qual ity standard have becn establ ished. Moreovcr, 65% bottled water companic pump watcr from any bore wcl l or mun icipal upply line, which may
calise depletion of groundwater duc to ovcr pumping, and pollute water sources
during puri fi ation processes. It i agreed that bottled water i of good quality, but the unavoidable contami nation incidents may take place at any t ime, leaving the
bottled water nOl suitabl e for drinking by human. FUlihem10re, good bottled water
quality does not imply good water qual ity source, however good water quality
sources l ike springs reduce the treatment needed, and consequently decrease the
water production cost (Ferrier, 200 1 ) .
The G u l f Standardization Organization (GSO) established standards for bottled water fit for human consumption, which is fo l lowed by a l l Gulf countries ( i nclud ing the U A E ) . The standards were modi fied through a technical gulf
comm ittee, and the draft report was prepared by the state of Qatar. I t was then
approved by the board of d irectors of the GSO in a meeting that was held in 2009. Bottled water i defined by GSO standards as "Treated drinking water intended
for human consumption, bottled in suitable tightly sealed containers and
complying w ith a l l the requirements mentioned in the standard report ' (GSO,
2009).
Before considering any water body as o fflcial water source suffic ient for
human use, severa l amples are tested, and the water source is approved by a
govemmental agency. Physical and chemical treatment methods should be IJsed,
and have to be adequate to remove a l l microbes from the water before being used 22
b y human. \\ ater i then tran ported from production p lace to packaging itc through control led equipment to avoid any pos ible contamination (GSa, 2009).
Physlcal 1 ropcliie ( i .e. taste, odor and co lor) and chem ical con tituents ( i . g. arsenic, barium, boron, chromium, manganese, molybdcnum selen ium and uranium) of bottled water are all being regulatcd. The pH of bott led watcr shou ld be between 6.5 and 8 , while the total dis o l ved sol ids (TDS) should be between 1 00 and 600 m g/L. Fluoride content shou ld be between 0 . 8 to I .S mg/L (GSa, 2009).
Chemicals used in water treatment or materials in contact with water are
a lso being contro l led. The max i mum al lowabl e level of antimony is 20 flg/L, while the l evel of v inyl chloride shou ld not exceed 0.3 flg/L. Chemicals present in water from industrial sources are also contro lled, as the maximum allowable level o f D H E P i 8 flglL. The maximum al lowable l i m i t for agriculture pesticide residue , and pesticide used in water for public health purposes range between 2 �l g/L for l indane and 20 fl g/L for trifl uralin. I f total radioacti ve components exceed 1 0 Bq/L, special tests are done to determ ine the levels of different radionuc l ides and control them (GSa, 2009).
Bottled drinking watcr shou ld be free from algae, molds, insects and a l l
types o f m icroorganisms. B ottled drinking water should also b e free from E-co l i ,
sulphite constituent, pseudomonas aeruginosa and fecal streptococc i during fi l l ing
and marketing i n evcly 250 ml sample examined. Routine and non-routine tests
are always carried out to assure tbat bottled water meet m icrobiological, chemical
and physical standards (GSa, 2009).
fi l l i ng operation should be done in hygien ic environment. Bottled water i packed In clean, aseptic. scaled containers to prescr\ e changes 111 i ts chemical and physical properties and inhibit any pos ible contamination. Bottled water should
bc protected from unlight and ele\ ated temperature during storage and transportation. It should al:o be stored in a room with good venti lation, and placed
away from any hanrdous or poi ning material and potential contamination (G a, 2009).
urce of
G s a require. proper bott led water label ing, including ' bottled drinking water" as the name of the product along with the brand name, d i fferent an ions ( i .e. h londe, SUlphate. nitrate, carbonate, bicarbonate and fluoride), cations ( i .e. calcium. magne ium, sodium, potassium, lotal hardness and total dissolved 'olid ) , water p H , volume of the bottle in metric system unit, fi l l i ng and expi ry date and any additives such a fluoride. Misleading statements about the nature and properties of the product are not al lowed. It is also recommended that detai led l ab e l i ng to be done on both , containers and cartoon boxes, where many water bottles are packed (GSa, 2009). For more information about bottled water regulation in the UAE, please refer to Append i x E .
2.4 PET BOTTL ES
Bottled water containers vary in shape and color. Variou types of bottled
water packaging have been llsed through h istory, starting with glass bottles that were 1I ed for a long time. Due to its heavy weight, glass was replaced by polyvinyl c hloride (PVC) in late 1 960s, which was again replaced by the l1lueh i mproved p lastic P ET in 1 9805. PET is brighter, more tran parent, does not break eas i l y and much more flexible than PVc. I t is 20% l ighter in weight than PVC, which makes it more econom ical as using the same amollnt of plastic aUows for
