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224 Q IWA Publishing 2009 Journal of Water and Health | 07.

2 | 2009

Endocrine disrupting compounds (EDCs) and


pharmaceuticals and personal care products (PPCPs) in
the aquatic environment: implications for the drinking
water industry and global environmental health
M. F. Rahman, E. K. Yanful and S. Y. Jasim

ABSTRACT

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) M. F. Rahman (corresponding author)
E. K. Yanful
are a group of chemical compounds with diverse physical and chemical properties. Recent Department of Civil and Environmental
Engineering,
studies have indicated undesired effects of EDCs and PPCPs at their reported trace
The University of Western Ontario,
concentrations (ng l21 to mg l21). This paper reviews the current knowledge on the sources, Spencer Engineering Building,
1151 Richmond Street,
properties, occurrence and health impacts of EDCs and PPCPs, and their removal from drinking London, Ontario,
Canada N6A 5B9
water using ozonation and ozone/hydrogen peroxide-based advanced oxidation. The paper also E-mail: mrahma49@uwo.ca

examines the potential threats posed by these chemicals to drinking water and public health.
S. Y. Jasim
While these compounds are known to have adverse effects on ecosystem health, notably in the Walkerton Clean Water Centre,
220 Trillium Court,
fish population, a similar link is yet to be established between ingestion of these compounds Building 3,
Walkerton, Ontario,
through drinking water and human health. In addition, data on the effectiveness of existing Canada N0G 2V0

methods for the removal of these compounds are not conclusive. Further studies are required to
characterize risks, and also to evaluate and optimize existing removal processes. Also concerted
international effort is urgent to cut down the risk of exposure and restrain the production and
marketing of toxic chemicals.
Key words | advanced ozonation, drinking water, EDCs, environmental health, PPCPs

ABBREVIATIONS POPs persistent organic pollutants


z
PPCPs pharmaceuticals and personal care products
OH hydroxyl radical
RO reverse osmosis
AOP advanced oxidation process
STP sewage treatment plant
BPA bisphenol-A
USEPA United States Environmental Protection Agency
DOC dissolved organic carbon
USGS United States Geological Survey
EDCs endocrine disrupting compounds
UV ultraviolet
EE2 17a- ethinylestradiol
GAC granular activated carbon
H2O2 hydrogen peroxide
NOM natural organic matter
INTRODUCTION
O3 ozone
PAC powdered activated carbon It was reported as early as 1930 that certain chemical
PAHs poly aromatic hydrocarbons compounds and plant tissues can have an impact on the
PCBs polychlorinated biphenyls hormone system (Walker & Janey 1930; Cook et al. 1934).
doi: 10.2166/wh.2009.021
225 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

With the advances in analytical capability, the presence of a compounds, poly aromatic hydrocarbons (PAHs) and
long list of chemically diverse compounds at trace concen- dioxins have so far been confirmed as EDCs. Drugs are
trations has been identified in the environment. Endocrine designed for specific biological action in target receptors
disrupting compounds (EDCs) and pharmaceuticals and (Halling-Sorensen et al. 1998; Jones et al. 2005). However,
personal care products (PPCPs) are almost ubiquitous in they can cause adverse impacts to non-target receptors
municipal sewage treatment plant (STP) effluents and (Jones et al. 2005; Jasim et al. 2006) and some of them
source waters for drinking water treatment plants (Snyder (certain oral contraceptive medications, thyroid hormones
et al. 2005). Many studies have indicted trace level administered as medications, and estrogen replacement
occurrence of EDCs and PPCPs causing adverse impacts pharmaceuticals) can act as EDCs. To date no exhaustive
in humans and in ecosystems. There is a perceived risk of list of EDCs exists, because, for many chemicals, there is
indirect contamination via drinking water as studies have limited and incomplete evidence of endocrine disrupting
shown that conventional treatment systems perform poorly activity or evidence of endocrine activity which is con-
in removing these chemicals from drinking water (Snyder troversial and also because most chemicals in the market
et al. 2003; Westerhoff 2003; Stackelberg et al. 2004). have not been tested for their endocrine toxicity (Snyder
Thus the drinking water industry faces a challenge as et al. 2006a; Kim et al. 2007).
regulatory bodies and the public become aware of the The endocrine system controls various basic functions
presence of these compounds in water, which were such as reproduction, synchronization of physical develop-
previously not detectable (Westerhoff 2003). This paper ment and maintenance in animals and plants with the help
attempts to provide a summary of the properties of EDCs of hormones (Lintelmann et al. 2003; Birklett 2003). Of the
and PPCPs, their occurrences in the aquatic environment, various mechanisms by which EDCs affect the hormone
health impacts, and discusses their removal from water system, the principal three (Pocar et al. 2003) are as follows.
using ozonation and ozone-based advanced oxidation. The They may act as a hormone mimic by binding to the
paper lists some of the challenges these micro-pollutants receptor sites of the target cells and activating a response.
present to the drinking water industry. It also discusses the This is defined as an agonistic effect. In the case of an
threats EDCs and PPCPs pose to public health, and antagonistic effect, the chemical will act as a hormone
addresses the current gaps in knowledge and future blocker and no response is produced as the chemical binds
research needs. It is hoped that this work would encourage to the receptor and prevents natural hormones from
readers from various disciplines to get involved and interacting. Figure 1 illustrates these endocrine disruption
contribute to the ongoing discussion on the presence of processes (agonistic and antagonistic effects). Sometimes
EDCs and PPCPs in the aquatic environment. agonists and antagonists bind to the same receptors
resulting in subtle changes in receptor conformation
(Birklett 2003).
EDCs and PPCPs found in the aquatic environment are
EDCS AND PPCPS: SOURCES AND PROPERTIES
structurally diverse. Water solubility, adsorption coefficient
EDCs are either naturally occurring or synthetic substances (log KOC), bioconcentration (log KOW) and Henry’s law
that interfere with the functioning of hormone systems constant (Birklett 2003; Lintelmann et al. 2003) are some
resulting in unnatural responses (Birklett 2003). The United of the important properties that determine the fate and
States Environmental Protection Agency (USEPA) defines behaviour of EDCs. A low water solubility and high
EDCs as agents that ‘interfere with the synthesis, secretion, octanol/water partition coefficient (log KOW) or high car-
transport, binding, or elimination of natural hormones in bon/water coefficient (log KOC) will promote sedimentation
the body that are responsible for maintenance of homeo- or association with biota (Birklett 2003). PPCPs are
stasis, reproduction, development and/or behaviour’ (Birk- biologically active, not readily biodegradable and often
lett 2003). A number of steroid hormones, both natural have high water solubility relative to their molecular weight
and synthetic, alkylphenols, pesticides, organic oxygen (Jorgensen 2001). Despite having short half-lives, many
226 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

Hormone Hormone Hormone mimic Hormone Hormone blocker

Cell Cell Receptor Receptor


Receptor Cell

Effector Effector Effector

Natural response Agonistic response Antagonistic response


(inhibited effect)

Figure 1 | Endocrine disruption process (from Birklett 2003).

PPCPs can still become persistent in the aquatic environ-


OCCURRENCES IN THE AQUATIC ENVIRONMENT
ment owing to their continual disposal and release in the
aquatic environment (Jasim et al. 2006). Herbicides constitute more than half of all pesticides used
EDCs and PPCPs find their way into watercourses by in the developed world (Hua et al. 2006a). A number of
many routes including direct discharges into water; studies have reported the occurrence of pesticides and
excretion and inappropriate disposal after use of drugs herbicides and their metabolites in surface water, ground-
and chemicals by householders; agricultural and cattle water and near-surface aquifers in the United States
feedlot runoff; industrial and STP effluents; accidental (Thurman et al. 1992; Kolpin et al. 1996, 1998a,b, 2000,
releases (through spills, run off, atmospheric deposition); 2002; Boxall et al. 2004). Kolpin et al. (1998a) detected
and release of compounds indirectly through diffuse sources pesticides including atrazine, metachlor and prometon, in
such as storm water runoff (Jones et al. 2004; Sumpter 2005; 54.4% of groundwater samples in 1,034 sites across the
Falconer et al. 2006). Moreover pollutants can be trans- United States. However, concentrations of the detected
ported via watercourses to new areas far from their sources, contaminants were generally less than 1 mg l21. Atrazine,
for example persistent organic pollutants (POPs) can of which about 3 £ 106 kg per year is used in the great
accumulate in areas such as the Arctic where they have lakes basin, has also been frequently detected in river
never been used or produced (Lintelmann et al. 2003). Due waters in Ontario, Canada (Frank & Logan 1988; Hua
to strict regulations, point sources such as manufacturing et al. 2006a,b; Jasim et al. 2006). A detailed survey
industries of both human and veterinary medicines do not conducted by the United States Geological Survey
contribute to pharmaceuticals pollution as much as non- (USGS) in 139 streams across 30 states in the United
point sources such as households and agricultural runoff States detected 82 of 95 target compounds that included
(Jones et al. 2003). About 33% of the total volume of drugs steroids, plasticizers, detergent metabolites, veterinary
and 25% of the total sold is disposed of with household medicines and other organic water contaminants. Steroids
waste or in drains in Germany and Austria, respectively and nonprescription drugs were the most frequently
(Kummerer 2004). A survey in the United Kingdom found detected contaminants with over 80% occurrence (Kolpin
that 63.2% of unwanted medicines are disposed of with et al. 2002).
household wastes and another 11.5% are flushed down the Metabolites of chemicals are also important; Boxall
sink or toilet (Bound & Voulvoulis 2005). Also a significant et al. (2004) reported occurrences of metabolites more
proportion of drugs may flush out of the human body frequently than their parent compounds. Acetachlor ESA
unmetabolized. For example, beta-blocker nadolol can be and acetachlor OXA were detected 30% more frequently
excreted unmetabolized, in contrast to carbamazepine, of than their parent compound acetachlor (Boxall et al.
which only 3% is excreted unchanged (Bound & Voulvoulis 2004). Similar conclusions were also drawn by Kolpin
2005). Table 1 lists some EDCs and PPCPs, and their main et al. (1998b). Degradates often have a much lower KOC
sources or pathways and important physicochemical value than their parent compounds. Thus those degra-
properties. dates are more likely to be released by STP effluents or be
Table 1 | Sources and physicochemical properties of selected EDCs and PPCPs

227
Water solubility@

M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment


Name Main source or pathways CAS registry no. Molecular weight 258C (mg l21) Log Kow

Steroids
Estrone (E1) 53–16–7 270.4 (Westerhoff 12.42 (Lintelmann 3.13 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Estriol 50–27–1 288.4 (Westerhoff 13.25 (Lintelmann 2.45 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Testosterone Plant & Davis (2003) Sewage treatment plant 58–22–0 288.2 (Westerhoff 5.57 (Lintelmann 3.32 (Lintelmann
(STP) effluents and agricultural runoff et al. 2005) et al. 2003) et al. 2003)
17b-estradiol (E2) 50–28–2 272.2 (Westerhoff 12.96 (Lintelmann 4.01 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
17a-ethinylestradiol 57–63–6 296.2 (Westerhoff 4.83 (Lintelmann 3.67 (Lintelmann
(EE2) et al. 2005) et al. 2003) et al. 2003)
Diethylstilbestrol (DES) 56–53–1 5.07 (Lintelmann
et al. 2003)
Alkylphenols
4-Nonylphenol Plant & Davis (2003) Surfactants, in certain 84852–15–3 220 (Ying 5.43 (Lintelmann 4.48 (Lintelmann
kinds of detergent. May enter environment et al. 2002) et al. 2003) et al. 2003)
via industrial and municipal effluents
Nonylphenol-ethoxylate 27986–36–3 264(Ying 3.02 (Lintelmann 4.17 (Lintelmann
et al. 2002) et al. 2003) et al. 2003)
4-tert-octylphenol 104–66–9 206 (Ying 12.6 (Lintelmann 4.12 (Lintelmann
et al. 2002) et al. 2003) et al. 2003)
Triazine herbicides
Atrazine Plant & Davis (2003) Widely used worldwide, 1912–24–9 215.1 (Westerhoff 30 @ 208C 2.61 (Westerhoff
mainly on maize. Enters by agricultural runoff as et al. 2005) (WHO 1996) et al. 2005)
diffuse pollution into groundwater. Non-agricultural
uses have been banned in developed countries
Simazine 122–34–9 201.7 5 @ 208C 2.18 (WHO 1996)
(Schwarzenbach (WHO 1996)

Journal of Water and Health | 07.2 | 2009


et al. 2003)
Organochlorines
p-p 0 DDT Plant & Davis (2003) May enter environment 50–29–3 354.5 (Westerhoff 0.0034 (Lintelmann 6.20 (Lintelmann
through groundwater, atmospheric transport and et al. 2005) et al. 2003) et al. 2003)
agricultural runoff. DDT is still being used in
some developing countries and may be concentrated
in imported goods. But main sources in developed
countries are likely to be historically contaminated sites
p-p 0 DDE 72–55–9 315.9 (Westerhoff 0.024 (Lintelmann 5.76 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Table 1 | (continued)

228
Water solubility@
Name Main source or pathways CAS registry no. Molecular weight 258C (mg l21) Log Kow

M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment


Dieldrin 60–57–1 380.9 (Westerhoff 0.186 @ 208C 6.2 (Health
et al. 2005) (Health Canada 1995) Canada 1995)
p-p 0 DDD 72–54–8 320.1 (Westerhoff 0.090 (Lintelmann 5.86 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Methoxychlor 72–43–5 344 (Westerhoff 0.045 (Lintelmann 4.68–5.08
et al. 2005) et al. 2003) (Lintelmann
et al. 2003)
Polyaromatic
hydrocarbons (PAHs)
Pyrene Lintelmann et al. (2003) Generated during 129–00–0 202.3 (Westerhoff 4.88 (Westerhoff
incomplete combustion of organic matter. et al. 2005) et al. 2005)
Emission from anthropogenic sources such
as traffic, heating and industrial processes like steel
and aluminium production. May also enter from
natural events such as volcanic eruption and
forest fire
Benzo[a ] pyrene 50–32–8 252.1 (Westerhoff 0.0033 (Lintelmann 6.13 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Fluoranthene 206–44–0 202.3 (Westerhoff 0.22 (Lintelmann 5.13 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Benzo[b ] fluoranthene 205–99–2 252.3 (Westerhoff 0.0012 (Lintelmann 5.78 (Lintelmann
et al. 2005) et al. 2003) et al. 2003)
Other substances
Bisphenol A Plasticizer, fungicide and disinfectant. May enter 80–05–7 228.29 120 (Lintelmann 3.4 (Lintelmann
via industrial effluents and also from products et al. 2003) et al. 2003)
in use and waste products
Bis (tributyltin)oxide Main source: harbours. Organotins used for 56–35–9 8–10 (Lintelmann 3.62 (Lintelmann
painting of ships et al. 2003) et al. 2003)
2,3,7,8- TCDD Plant & Davis (2003) Diffuse sources including metal 1746–01–6 321.9 (Arthur & 0.0013 £ 1023 6.76 (Lintelmann

Journal of Water and Health | 07.2 | 2009


processing industries, medical and other waste Frea 1989) (Lintelmann et al. 2003)
incineration et al. 2003)
2,3,7,8-TCDF 51207–31–9 306 (Schwarzenbach 0.00042 (Lintelmann 6.22 (Lintelmann
et al. 2003) et al. 2003) et al. 2003)
Pharmaceuticals
Carbamazepine STP effluents: domestic use, excretion and 298–46–4 236.28 (Nentwig 17.7 (Nentwig 2.45 (Nentwig
inappropriate disposal. Failure of the STPs et al. 2004) et al. 2004) et al. 2004)
to efficiently remove these trace organic
compounds leads to their aquatic occurrences
229
M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment
Table 1 | (continued)

Water solubility@
Name Main source or pathways CAS registry no. Molecular weight 258C (mg l21) Log Kow

Caffeine 58–8–2 194.2 (Westerhoff Slightly soluble ,0 (Westerhoff


et al. 2005) et al. 2005)
Acetaminophen 103–90–2 151.2 (Westerhoff 0.46 (Westerhoff
et al. 2005) et al. 2005)
Ibuprofen 15687–27–1 206.1 (Westerhoff 21 (Scheytt 3.97 (Westerhoff
et al. 2005) et al. 2005) et al. 2005)
Naproxen 22204–53–1 230.1 (Westerhoff 27 (Mura 3.18 (Westerhoff
et al. 2005) et al. 2002) et al. 2005)
Gemfibrozil 25812–30–0 250.2 (Westerhoff 4.77 (Westerhoff
et al. 2005) et al. 2005)
Erythromycin-H2O 114–7–8 733.9 (Westerhoff Slightly soluble 3.06 (Westerhoff
et al. 2005) et al. 2005)
Trimethoprim 738–70–5 290.1 (Westerhoff 0.91 (Westerhoff
et al. 2005) et al. 2005)
Clofibric acid 882–09–7 214.65 (Nentwig 583 (Nentwig 2.57 (Nentwig
et al. 2004) et al. 2004) et al. 2004)
Iopromide 73334–7–3 790.9 (Westerhoff ,0 (Westerhoff
et al. 2005) et al. 2005)

Journal of Water and Health | 07.2 | 2009


230 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

transported to surface and ground waters from the soils. promoter, in drinking water at a concentration of 0.6–
Persistent and mobile degradates are often difficult to 1.7 ng l21.
identify and the costs associated with their analysis can EDCs such as bisphenol A (BPA), alkylphenols,
be high (Boxall et al. 2004). phthalates and PAHs can leach into drinking water when
About 100 pharmaceuticals have now been detected in plastics pipes are used in supply lines. BPA is used for
rivers, lakes and coastal waters throughout Europe and relining drinking water supply lines and as coatings for
the United States in trace concentrations (Hemminger many fittings. Concentrations of BPA up to 1 mg l21 have
2005). Analgesics (ibuprofen, naproxen), lipid regulators been reported in water supplies. BPA may also leach from
(gemfibrozil, clofibric acid), antibiotics, steroid hormones, lacquer in food cans into water supplies (Gomes & Lester
anti-epileptics (carbamazepine), X-ray media contrasts 2003). PAHs can be remobilized into the drinking water
(iopromide), stimulant caffeine and detergent metabolites when water mains are coated with coal-tar pitch. Maier et al.
have been reported in the concentration range of a few (2000) as cited by Gomes & Lester (2003) noted that
ng l21 to mg l21 in various water matrices including surface disinfection with chlorine might lead to the leaching of
waters and STP effluents (Halling-Sorensen et al. 1998; PAHs from coal-tar pitch.
Ternes 1998, 2001; Stumpf et al. 1999; Kolpin et al. 2002;
Metcalfe et al. 2003; Solaiman et al. 2004; Servos et al. 2005).
Bioaccumulation of 17a-ethinylestradiol (EE2) and nonyl-
HEALTH EFFECTS OF EDCS AND PPCPS
phenol in biota samples (Mediterranean mussels) in Venice
lagoon, Italy, in the concentration range of 7.2– 240 ng l21 Exposure to EDCs and PPCPs can result from chronic dose
have been found (Pojana et al. 2007). rather than bioaccumulation, thus making them toxic to
Available occurrence data for EDCs and PPCPs in receptor organisms. Fish probably bear the brunt of
drinking water are sparse (Snyder et al. 2005). Stackelberg occurrence of the chemicals in the aquatic environment.
et al. (2004) studied the occurrence of organic wastewater Impaired reproduction and sexual anomalies have been
contaminants in a United States drinking water treatment observed in some fish species. Some of the reported adverse
plant. Of the 106 target contaminants, 34 contaminants health impacts of EDCs and PPCPs on wildlife are
were detected in 10% of the raw water samples and more presented in Table 2.
than 11 contaminants (such as bisphenol A, carbamazepine, In recent years, incidences of breast, prostate and
caffeine, cotinine, tetrachloroethylene) in finished drinking testicular cancers have increased a great deal. This
water (Stackelberg et al. 2004). DEET (an insect repellent) increase has been linked to the EDCs (Plant & Davis
was found as the most common contaminant in both raw 2003). The consequences of prenatal exposure to diethyl-
and finished drinking water in recent research by the stilbestrol, such as reproductive disorders, cognitive
American Wastewater Research Foundation (Khiari 2007). impairment and miscarriage have been reported (Birn-
The foundation also reported frequent occurrences (.65% baum 1994; Damgaard et al. 2002; Falconer et al. 2006;
of samples) of ibuprofen, meprobamate, dilantin and Inadera 2006). Exposures to industrial chemicals and
iopromide in finished drinking water. Atrazine occurred at organochlorine pesticides have often been blamed for
the highest concentrations of any contaminant tested in causing early onset of puberty in girls, delayed puberty in
both raw and finished water but far below the maximum boys and impaired fertility in men (Sharpe & Irvine 2004;
21
contaminant level of 3 mg l (Khiari 2007). In Ontario, Snyder et al. 2005). Colon et al. (2000) detected high
Canada, ibuprofen was detected in finished drinking water levels of phthalate esters in Puerto Rican girls with
with a median concentration of 0.5 ng l21 and 13 ng l21 premature breast development (premature thelarche).
when the sources of water were lakes and rivers, respect- Prolonged or permanent neurological injuries including
ively, which were contaminated with upstream STP efflu- cognitive impairment and behaviour abnormalities may
ents (Metcalfe et al. 2004). Zuccato et al. (2000) reported occur in children, particularly to the foetus if exposed to
the occurrence of the antibiotic tylosin, a veterinary growth dioxins and PCBs (Falconer et al. 2006).
231
M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment
Table 2 | Reported health impacts of EDCs and PPCPs on wildlife

Species Health effects Environmental exposure/indicted contaminant References

Fish Mosquito fish Masculinization Exposure to androgenic Paper mill effluents. Howell et al. (1980),
Sumpter (2005) and Orlando
& Guillette (2007)
Rainbow trout Feminization (male fish producing Ethinyl-estradiol (EE2) and alkylphenol Purdom et al. (1994)
eggs and female hormones such as ethoxylates present in sewage treatment
vitellogenin) and sterility plant (STP) effluents
Alligators Reproductive tracts disorder including Organochlorines such as DDTs, DDEs Guillette et al. (1994)
reduced penis size in males and and Safe (2000)
population decrease
Gulls, terns, Feminization and other sexual Polychlorinated biphenyls Safe (2000) and Fry (1995)
herons and other abnormalities, thin walled eggshells (PCBs), DDTs, DDEs
predatory birds
White-backed Kidney failure leading to death. Veterinary use of diclofenac Proffitt & Bagla (2004)
(Gyps bengalensis) These species are on the verge
and long-billed of extinction in South Asia
(Gyps indicus) vultures
Snails Imposex (altered sexual orientation) Exposure to tributyltin (TBT) in marine Sumpter (2005), Sharpe &
environment near ports Irvine (2004) and Lintelmann
et al. (2003)
Daphnia pulex Impaired reproduction Simazine Falconer et al. (2006)
Ewes/sheep Infertility Observed in sheep that were grazed in Adams (1990)
clover pastures rich in phytoestrogen.

Journal of Water and Health | 07.2 | 2009


Formononetin in clovers is primarily
held responsible
232 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

In the Great Lakes area close to the Aamjiwnaang First carbon content and functional group composition (Wes-
Nations reserve near Sarnia, Ontario, Canada, fish with terhoff 2003; Jasim et al. 2006; Stackelberg et al. 2007).
intersex gonads (both male and female) have been reported Conventional treatments such as coagulation, sedimen-
in Lake St Clair (Kavanagh et al. 2004). The Polluted tation and filtration have been found to remove less than
Children, Toxic Nation study released by Environmental 25% of most EDCs and PPCPs and are largely ineffective for
Defense (2006) reported that the abnormality in reproduc- removing dissolved organic contaminants (Westerhoff 2003;
tive systems in this area may be occurring in humans as Vieno et al. 2006; Kim et al. 2007). Stackelberg et al. (2007)
well, as indicated by declining boy to girl sex ratios. found that clarification process with ferric chloride (FeCl3)
The study observed the accumulation of chemicals, such as coagulant accounted for the removal of only 15% of the
as PCBs and organochlorine pesticides (e.g. DDT) in average concentration of organic contaminants during
residents. Of the reported chemicals, 23 are already listed drinking water production at a US drinking water treatment
as EDCs (Environmental Defense 2006). Declined sperm facility. The removal of diclofenac, ibuprofen, benzafibrate,
counts, sperm quality and sex ratios in Canada and the carbamazepine and sulfamethoxazole by ferric sulphate-
United States have also been reported (Allan et al. 1997; assisted coagulation in both milliQ water and natural water
Safe 2000; Mackenzie et al. 2005). In Canada the sex ratio is was studied by Vieno et al. (2006). All the PPCPs studied
generally reported to be 105 liveborn male births to 100 showed poor removal (,10%), except diclofenac (66%).
liveborn female (m ¼ 0.512) (Allan et al. 1997). In Aamjiw- Free chlorine and chloramines can treat a range of EDCs
naang the sex ratio was reported to be m ¼ 0.348 during and PPCPs, mainly hydrophilic compounds (Stackelberg
1999– 2003 (Mackenzie et al. 2005). During 1970 – 1990 the et al. 2007; Snyder 2008). However, free chlorine is much
proportion of Canadian males declined by 2.2 live births per more efficient than chloramines at removing EDCs and
1,000 live births (Allan et al. 1997). PPCPs (Khiari 2007; Snyder 2008).
However, a number of studies have ruled out substantial Advanced water treatment technologies such as ozona-
changes in sperm counts and male reproductive capacity. tion, granular activated carbon (GAC) adsorption, and
Also many have suggested that association of organochlor- ultraviolet (UV) irradiation have shown promise in remov-
ines and xenoestrogens in female breast cancer is not likely ing EDCs and PPCPs. For UV treatment, a typical
(Safe 2000). Possible human health impacts from EDCs via disinfection dose of (5– 50 mJ cm22) was found to be several
drinking water have been refuted by several scientists as orders of magnitude lower than doses required for the
reported concentrations of those chemicals in water are removal of most chemicals (Snyder et al. 2003; Westerhoff
much lower compared with phytoestrogens and other 2003; Khiari 2007; Snyder 2008). USEPA recommends GAC
estrogenic compounds present in food sources (Safe 2000; as the best available treatment for removal of many
Snyder et al. 2003). Thus there still remains a debate endocrine disrupting compounds including methoxychlor,
concerning the impacts of EDCs and xenoestrogens on endosulfan, DDT and polychlorinated biphenyls (USEPA
humans and this glaring gap in knowledge clearly demon- 2001). However, there are several drug compounds with
strates the need for further research. high water solubility and/or poor degradability that can be
resistant to GAC (Jones et al. 2005). Iopromide, ibuprofen,
naproxen and dichlofenac, sulfamethoxazole and meproba-
mate are some compounds that were found to be recalci-
REMOVAL OF EDCS AND PPCPS FROM DRINKING
trant for activated carbon removal (Khiari 2007). Powdered
WATER: OZONE-BASED OXIDATIVE TREATMENT
activated carbon (PAC) is less expensive than GAC but is
The removal or degradation of organic contaminants labour intensive and is less efficient (USEPA 2001).
present in drinking water depends on several factors However, PAC can be very useful in short-term applications
including source water quality, treatment processes and such as for removal of pesticides after the first storm
goals, and intrinsic chemical properties of contaminants following their applications (USEPA 2001). Reverse osmosis
such as molecular weight, relative hydrophobicity, aromatic (RO) and nanofiltration have been found to be highly
233 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

effective in removing EDCs and PPCPs (Snyder et al. 2006a; commonly used in drinking water treatment (Von Gunten
Snyder 2008). But they are very costly and a portion of the 2003). AOPs are environmentally friendly as they neither
water is lost as brine. Disposal of brine is a significant generate substantial amounts of hazardous sludge nor
problem (Snyder et al. 2005) and the finished water has a transform pollutants from one phase to another (Gultekin
corrosive nature (Westerhoff 2003). Thus most drinking & Ince 2007).
water treatment facilities are not likely to install RO Ozone concentration, zOH radical concentration and
(Westerhoff 2003). second order rate constants for the reaction of the target
A number of studies have shown that ozone treatment compounds with molecular O3 (KO3 ) and zOH radicals
or ozone-based advanced oxidation treatment of water or (KOH) are the three factors which govern the oxidation of
wastewater can successfully reduce or eliminate EDCs and target compounds during ozonation (Ternes et al. 2002; Von
PPCPs. This paper discusses several aspects of ozone-based Gunten 2003; Huber et al. 2005). Chemicals containing
treatment and summarizes the results of selected previous phenolic groups, deprotonated amines and double bonds
studies. Ozone primarily is used for disinfection purposes in tend to show high oxidation rate constants with molecular
drinking water treatment. It can also bring secondary O3. Fortunately these functional groups are common
benefits including the removal of organic contaminants, constituents of many PPCPs (Mcdowell et al. 2005;
colour, taste, odour, iron and manganese. Ozone (O3) Westerhoff et al. 2005; Rakness 2005). Generally com-
attacks organic contaminants either by direct reaction (as pounds with KO3 . 104 M21s21 can be considered as fast
molecular O3), or through the formation of free radicals, reacting with ozone and thus are expected to show rapid
such as the hydroxyl radicals (zOH). O3 is a selective degradation during ozonation (Von Gunten et al. 2006).
oxidant; some organic contaminants are oxidized readily Second order reaction rate constants of some organic
and others are not oxidized at all (Von Gunten 2003). On compounds and pharmaceuticals are listed in Table 3.
the other hand, the zOH radical, the most powerful oxidant High KO3 values of carbamazepine, dichlofenac, EE2,
after fluorine, is non-selective and can oxidize a broad range sulfamethoxazole and roxithromycin indicate that these
of organic and inorganic compounds (Von Gunten 2003; pharmaceuticals will react with ozone quickly and undergo
Gultekin & Ince 2007). Oxidation of organic compounds by rapid transformation (Huber et al. 2003). On the other
ozone or zOH radicals results in the formation of simpler hand, compounds such as atrazine, geosmin, iopromide,
organic molecules that are readily biodegradable and may diazepam and ibuprofen have higher KOH values and lower
be withdrawn by biological filters (Von Gunten 2003; KO3 values, suggesting that AOPs would perform better in
Rakness 2005). removing them.
The advanced oxidation process (AOP) involves the Water matrices can also have a significant effect on
oxidation of target contaminants by zOH radicals (Rosen- oxidation of organic compounds. Dissolved organic carbon
feldt et al. 2006). In ozone/hydrogen peroxide-based AOP, (DOC) and alkalinity of natural water control O3 stability,
hydrogen peroxide (H2O2) initiates and propagates the and formation and scavenging of zOH radicals (Huber et al.
decomposition of ozone, which in turn, generates zOH 2003). Also ozone stability depends on pH (Von Gunten
radicals through a series of complex reactions that can 2003). It has been observed that ozone half-life is signifi-
increase the concentration of zOH radicals (Rakness 2005). cantly higher in natural water with high alkalinity and low
Thus AOPs may effectively remove organic compounds that DOC compared with water with low alkalinity and high
are recalcitrant to ozone alone. Also ozone-based AOPs DOC (Acero & Von Gunten 2001; Huber et al. 2003).
would cut down the reaction time and allow application of Typically zOH exposure is lower at higher alkalinity due to
higher ozone dosages without leaving excessive ozone to be the increased OH scavenging rate of carbonate, and higher
quenched at the outlet of the reactor (Von Gunten 2003). at lower natural organic matters (NOM) concentration
Increasing the reaction time after ozone addition or raising (Rakness 2005). Thus AOPs in natural waters with high
the pH can also enhance AOPs. However addition of H2O2 ozone stability (that is low DOC and high alkalinity) can
is cheaper than the other two options and is, therefore, most considerably increase the oxidation of O3 recalcitrant
Table 3 | Oxidation kinetics of some organic compounds with ozone and OH radicals

234
Compound/Class Use pKa Reactive group KO3(M21s21)* KOH 3 109 (M21s21) Reference

M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment


17a- Ethinylestradiol (EE2) Steroid hormone 10.4 Phenol ,7 £ 109 9.8 ^ 1.2 Huber et al. (2003)
Benzafibrate Lipid regulator 3.6 R-oxy group 590 ^ 50 7.4 ^ 1.2 Huber et al. (2003)
Carbamazepine Anti-epileptic Double bond ,3 £ 105 8.8 ^ 1.2 Huber et al. (2003)
Diazepam Anti-epileptic 0.75 ^ 0.15 7.2 ^ 1.0 Huber et al. (2003)
Dichlofenac Analgesic 4.2 Aromatic amine ,1 £ 106 7.5 ^ 1.5 Huber et al. (2003)
Ibuprofen Analgesic 4.9 9.6 ^ 0.1 7.4 ^ 1.2 Huber et al. (2003)
Iopromide X-ray contrast media ,0.8 3.3 ^ 0.6 Huber et al. (2003)
Sulfamethoxazole Antibiotic 5.7 Aromatic amine ,2.5 £ 106 5.5 ^ 0.7 Huber et al. (2003)
Roxithromycin Antibiotic 8.8 Tertiary amine (4.5 ^ 0.5) £ 106 Huber et al. (2003)
Atrazine (ATRA) Pesticides 6.0 3.0 Acero et al. (2000)
ATRA-imine Degradation products ,1 1.7 Acero et al. (2000)
of ATRA
DEA 0.18 1.2 Acero et al. (2000)
DIA 3.1 1.9 Acero et al. (2000)
MTBE Fuel additive 0.14 1.9 Von Gunten (2003)
(at ambient temperature)
Geosmin Algal product ,10 8.2 Von Gunten (2003)
(at ambient temperature)
2 Methylisoborneol (MIB) Algal product ,10 3 Von Gunten (2003)
(at ambient temperature)
Ciprofloxacin Antibiotic 0.4 £ 103 4.1 ^ 0.3 Vieno et al. (2007)
Estimated rate constants of PPCPs and
EDCs that are expected to show high
reactivity with molecular ozone
Beta blockers Beta blocker Amine (1– 10) £ 103 Huber et al. (2003)
Fluoroquinolones Antibiotic Amine (1– 10) £ 103 Huber et al. (2003)
5
Macrolides Antibiotic Amine .10 Huber et al. (2003)

Journal of Water and Health | 07.2 | 2009


Sulfonamides Antibiotic Amine .105 Huber et al. (2003)
Tetracyclines Antibiotic Phenol (1– 10) £ 106 Huber et al. (2003)
6
Triclosan Antimicrobial Phenol .10 Huber et al. (2003)
Oxybenzone Sunscreen agent Phenol (1– 10) £ 106 Huber et al. (2003)
Estradiol Hormone Phenol 106 Huber et al. (2003)
5
Testosterone Hormone Double bond 10 Huber et al. (2003)
4-nonyl phenol Detergent metabolite Phenol (1– 10) £ 106 Huber et al. (2003)
6
Bisphenol-A Plasticizer Phenol (1– 10) £ 10 Huber et al. (2003)
*T ¼ 208C.
235 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

pharmaceuticals (Huber et al. 2003). Ozone stability in within 1.3 minutes with an O3 residual of less than
natural water is difficult to assess, as the effect of NOM is 0.05 mg l21. Acero et al. (2000) found that O3/H2O2 can
variable and unknown. It can act as both an initiator and an significantly accelerate the rate of degradation of atrazine
inhibitor of ozone decomposition and scientists are yet to be compared with O3 alone. While conventional ozonation
able to estimate the fractions of NOM responsible for with an ozone dose of 2 mg l21 took 30 minutes to reach
promotion or inhibition of ozone decay (Von Gunten 2003). 60% degradation, it took only 2 minutes to reach the same
Huber et al. (2003), however, observed that, regardless of level of degradation when 0.8 mg l21 H2O2 was combined
the water matrix, relatively low ozone doses (0.5– 2 mg l21) with an ozone dose of 2 mg l21 (Acero et al. 2000). Zweiner
are sufficient for complete transformation of pharmaceu- & Frimmel (2000) reported 90% removal of clofibric acid,
5 21 21
ticals with KO3 . 10 M S . In the case of AOPs, an ibuprofen and dichlofenac using a 3.7 mg l21 O3 dose
initial O3 concentration similar to the DOC value of the coupled with 1.4 mg l21 H2O2 and more than 98% removal
water matrix might ensure availability of sufficient ozone for at a concentration of 5 mg l21 O3 and 1.8 mg l21 H2O2.
reaction with H2O2 (Zweiner & Frimmel 2000). In Vieno et al. (2007) were able to reduce the concentration of
summary it can be observed that the overall efficiency of most of their target compounds, which included beta
AOPs and ozonation would largely depend on the zOH blockers, anti-epileptic drugs and anti-inflammatory drugs,
radical scavenging capacity of natural water, NOM content below the detection limit following an ozone dose of
and type, and oxidation reaction kinetics of the targeted 1 mg l21. Ciprofloxin was found to be the most obstinate
chemicals (Zweiner & Frimmel 2000; Huber et al. 2003; compound in their study (Vieno et al. 2007).
Von Gunten 2003). A PPCPs and atrazine removal study at the A.H. Week
The removal of clofibric acid, benzafibrate, carbamaze- drinking water treatment plant in Windsor, Canada, found
pine, primidone and dichlofenac during drinking water that, while conventional coagulation/flocculation/sedimen-
treatment was investigated by Ternes et al. (2002). While tation and dual media filtration treatment were largely
dichlofenac and carbamazepine were almost completely ineffective, ozonation followed by conventional treatment
21
eliminated at an ozone dose of 0.5 mg l , removal of substantially enhanced the removal of carbamazepine,
clofibric acid was # 40% even at elevated ozone doses of continine, caffeine and atrazine (Hua et al. 2006a). The
21
2.5– 3.0 mg l . Moderate removal for benzafibrate and mean elimination ranges for carbamazepine, continine,
premidone were observed with 50% removal at ozone caffeine and atrazine were 78 – 99%, 83 – 93%, 67 – 81%
21 21
doses of 1.5 mg l and 1.0 mg l , respectively, and and 66 – 96%, respectively (Hua et al. 2006a). Snyder et al.
removals of . 80% at an ozone dose of 3.0 mg l21. Another (2006b) studied the removal of 36 different EDCs and
study by Ternes et al. (2003) found X-ray contrast media PPCPs in both surface water and wastewater using O3 and
such as iopromide, iopamidol, diatrizoate, and iomeprol O3/H2O2. Ozone doses of 1.25 mg l21 or greater were found
were extremely recalcitrant at an ozone dose of 5 mg l21. to be sufficient to achieve more than 80% removal of 22
Diatrizoate was the most recalcitrant compound showing compounds in surface water. Results of the study indicate
21
only 36% removal even at 15 mg l O3 dose. Nakada et al. that use of O3/H2O2 could reduce the contact time required
(2007) studied the removal of 24 PPCPs during sand by O3 alone. However, given sufficient contact time the
filtration and ozonation at a STP. They observed that sand overall removal using O3/H2O2 will probably not increase
filtration was generally inefficient in removing the target significantly and might even lead to a net decrease in
pollutants. Ozonation on the other hand attenuated the contaminant removal (Snyder et al. 2006b). Addition of
concentration of the phenolic antiseptics, sulfonamide H2O2 to O3 showed slightly higher removal for most
antibiotics and 17b-estradiol (E2) by 80% or above. compounds but for certain compounds, such as androste-
Jasim et al. (2006) observed a 67 –96% removal of nedione, progesterone, testosterone, caffeine, metolachlor
atrazine following ozonation compared with only 0 – 13% and pentoxifylline, overall removal was 15% lower com-
removal in conventional treatment. Almost 95% elimination pared with O3 alone (Snyder et al. 2006b). Also disinfection
of all target antibiotics was achieved by Adams et al. (2002) by zOH radicals is poor compared with O3 and there is a
236 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

possibility of forming additional disinfection by-products investment and skilled labour, and the public may not be
(Snyder et al. 2006b; Wert et al. 2007). willing to pay for the extra cost for risks that have not been
To date little is known about the formation, fate, well established (Snyder et al. 2005). Furthermore, contami-
detection and toxicity of oxidation by-products of EDCs nation will vary from region to region and will probably
and PPCPs (Westerhoff 2003). Bromate, which does not change with time as well, depending upon the use of specific
undergo degradation in biological filters, is the only by- chemicals or medicines. For example clofribric acid, a lipid
product of ozonation regulated in drinking water treatment regulator, is no longer widely used in North America and thus
(Von Gunten 2003). Huber et al. (2003) noted that typical its occurrence in North American waters compared with
ozone doses for removing fast reacting pharmaceuticals Europe is sparse (Betts 2002; Boyd et al. 2003).
would not produce significant amounts of bromate. Ozonation and ozone-based AOPs have significant
Although the target of the ozonation is to degrade the potential for removing EDCs and PPCPs from drinking
parent compounds to effectively reduce their biological water. Unfortunately, data on the efficiency of ozonation
activity, Vieno et al. (2007) noted that recent studies have and advanced oxidation processes in removing these
observed that this goal might not always be achieved. contaminants are not conclusive (Betts 2002). Moreover
Quinolone, which is primarily responsible for the pharma- economically feasible ozone doses will probably form
cological effect of ciprofloxacin, is not attacked by ozone by-products that could also be toxic (Snyder et al. 2006b).
(Vieno et al. 2007). Thus by-products of oxidation of EDCs However, as NOM concentration in natural waters is
and PPCPs are of concern since they might as well be toxic several magnitudes higher than trace contaminant concen-
(Huber et al. 2003; Snyder et al. 2006b; Vieno et al. 2007). trations, it is probably more prudent to prioritize research
on by-product toxicity from NOM rather than those from
trace contaminants (Snyder et al. 2006b). The cost of the
operation of advanced treatment technologies might seem
CHALLENGES POSED BY EDCS AND PPCPS TO THE
expensive even in some communities in the developed
DRINKING WATER INDUSTRY
world. Thus advanced water treatment technologies for
Currently there exist no regulatory guidelines to control the the removal of EDCs and PPCPs might seem a luxury for
occurrence of EDCs and PPCPs in the environment. most developing countries as their water quality pro-
Moreover, a significant portion of the contamination is grammes are already combating a wide range of problems
occurring from non-point sources. With growing public and are doing so in an economic environment that is
concern at the presence of EDCs and PPCPs in water, the severely restricted. Removal of EDCs and PPCPs can occur
drinking water industry faces a challenge as to which through natural phototransformation or biotransformation,
compounds should be treated and to what level they should which is increased considerably during summer (Vieno et al.
be treated as maximum contaminant levels are not known 2007). For many hot climate countries where adequate
(Jasim et al. 2006). sun is available for longer periods of the year, this could
Extremely low concentrations of these compounds in the be a viable option for removal of EDCs and PPCPs in
environment pose an analytical challenge (Snyder et al. lagoons and research should be directed towards how to
2005). Although there have been some recent advances in maximize the photo-transformation of micro-pollutants
analytical methods (Westerhoff 2003), differing polarities using natural light.
and functionalities of various compounds still make it hard Comparison of daily or life intake of pharmaceuticals via
to identify them at a concentration range of mg l21 to ng l21. drinking water (2 litres per day over 70 years) with
Moreover, very few laboratories have the necessary facilities therapeutic doses indicates that the exposure levels are low
to analyse them and costs can be substantial (Snyder et al. and well below the dosages that can cause pharmacological
2005). As these compounds have varying composition and effect (Webb et al. 2003). However, one potential concern is
physicochemical properties, their removal requires advanced the presence of cytotoxic drugs such as anti-neoplastics
treatment processes which would need significant capital (e.g. cyclophosphamide), which are carcinogenic, teratogenic
237 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

and risks may exist at any level of exposure (Webb et al. Concentrations (ng g21) of DDTs found in breast milk in Iran,
2003). The use of therapeutic doses to estimate the risk thus China, Turkey and Mexico were 3 – 27 times higher than
may not be applicable to genotoxins such as cyclopho- those found in countries such as Japan, Canada, Sweden
sphamide (Webb et al. 2003). Moreover, at present, and Germany (Kunisue et al. 2004). Often chemicals or drugs
individual toxicity of a compound is considered while that are expired or have been banned from the market or
setting up drinking water guidelines, but the synergistic, fail to register in the industrialized countries find their way
long-term, low concentration effect of multiple organic to markets in developing countries (Jamall & Davis 1991;
compounds present in water is not known (Stackelberg Okeke et al. 1999). For example, between 1987 and 1989,
et al. 2004). manufacturers in the United States produced and exported
Due to the soaring demand for water and depleting nearly 5,000,000 pounds (2,290,000 kg) of the insecticides
fresh water resources, artificial ground water recharge with chlordane and heptachlor, which had already been banned
STP reclaimed water is being considered in many parts of in the United States (Jamall & Davis 1991). As most deve-
the world, in arid regions in particular. However, there is loping countries are still fighting more immediate problems
increasing concern that groundwater recharge would such as water supply, sanitation, waste disposal, war and
contaminate groundwater with EDCs and PPCPs (Betts famine, in many of these countries the long-term risk of
2002). Factors such as location of the treatment plant, EDCs may not be seen as a pressing issue at the present time.
treatment technologies used at the drinking water treatment Smith (2000) questioned ‘If malaria were killing a million
facility and the relative degree of contamination of the people a year in North America and Europe, would the
source water greatly influence the contamination profile case for globally banning DDT be argued so forcefully?’. Thus
and concentration in finished drinking water (Metcalfe et al. to strike an optimum balance in meeting the goals of
2004). Given the current paucity of data and the fact that protecting human health and conserving the environment,
the contamination from EDCs and PPCPs differs geographi- it is necessary for the scientific community to look for low cost
cally and temporally, it is necessary that further research be sustainable alternatives to these chemicals (Seagren 2005).
directed to detect the level of occurrence of EDCs and The reported incidences of hormone-related cancers are
PPCPs in raw water, to determine temporal and spatial significantly higher in industrialized countries. For example,
factors influencing the contamination of raw water and death from breast cancer is almost ten times higher in North
effects of the treatment technologies used in the production America and Northern Europe compared with Asia and
of drinking water (Metcalfe et al. 2004). Africa (Sasco 2003). Incidences of hormone-related cancers
are also increasing in the developing world but are probably
under-reported. For example in Punjab, Pakistan, there has
been a sharp rise in cancer patients in the area. Elevated
EDCS AND PPCPS: IMPLICATIONS FOR GLOBAL
serum levels of endocrine-disrupting pesticides were
ENVIRONMENTAL HEALTH
detected in farmers in the same area (Ejaj et al. 2004).
Contamination of the aquatic environment by EDCs and Estimates show that there are about 20,000 deaths each
PPCPs has raised concerns over threats to public health year in the world due to acute pesticide intoxication, 99% of
and ecosystems. Such contamination can easily defy which probably take place in developing countries where
geographical boundaries and contaminate newer areas, as is only 20% of agro-chemicals are used (Jamall & Davis 1991;
the case with persistent organic pollutants. Some of the Vineis 2000). Pesticides have often been reported to induce
organochlorine pesticides, which are already banned in immune dysfunction. Environmental estrogens have the
industrialized countries, are still being used to fight diseases potential to bioaccumulate in body fat and may sub-
such as malaria in developing countries. High levels of sequently amount to a considerable dose (Ahmed 2000).
organochlorine pesticides have been identified in the They may be released from body fat during starvation and
environment and, also, in human breast milk in many can also enter infants during pregnancy or through breast
developing countries (Kunisue et al. 2004; Minh et al. 2006). milk. This could lead to a bi-directional interaction between
238 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

the immune system and the endocrine system. EDCs may learning disabilities, congenital malformations and cancers
alter the reproductive system, which in turn may affect the as the leading causes of death (Suk et al. 2003). It is
immune system and vice versa (Ahmed 2000). A significant probably the exposure to synthetic chemicals in the air,
portion of the population in developing countries is under water, soil and food chain that are contributing to the
the stress of malnutrition and infectious diseases. Environ- changing patterns of paediatric diseases, especially the
mental toxins would interact with malnutrition and infec- increasing incidences of chronic diseases in children.
tious disease to magnify their individual impact and, also, The availability of cheap child labour, the lack of occu-
the impact on the immune system (Jamal & Davis 1991). pational and environmental protection in conjunction with
Moreover, lack of a regulatory framework to minimize the constant export of hazardous chemicals and toxic wastes
exposure to chemicals exacerbates the pollution scenario in from industrialized countries to developing countries have
those regions of the world (Jamall & Davis 1991). placed children in those regions at a twofold risk of
Thus people in developing countries are often at higher infectious diseases and chemical hazards (Suk et al. 2003).
risk of exposure to toxicants leading to adverse health The health implications of the exposure to toxic chemicals
effects (Craft et al. 2006). for children is considerably higher compared with adults as
One particular concern with PPCPs in water is the their developing systems are more delicate and they might
global rise of antibiotic resistance. Antibiotics may escape not be able to repair the damage that is triggered by early
the STPs, find their way to the watercourses and increase exposure to toxicants (Suk et al. 2003).
resistance in natural bacterial populations (Jones et al.
2003). Tamiflu, the effective antiviral for avian influenza,
can escape STPs and even UV radiation cannot substan-
CONCLUDING REMARKS
tially degrade it (Fick et al. 2007). Thus there is a concern
that tamiflu and its metabolites (especially oseltamivir The risk of water borne diseases still prevails in many parts
carboxylate) may be released into the aquatic environment of the world. Emerging technologies such as ozonation will
and lead to increased resistance in the bird-flu virus. Poor probably not be able to totally replace chlorine as a water
quality antibiotics including degraded and expired anti- purifier and disinfectant (Shiru 2000). Although data on
biotics, misuse and overuse of antibiotics by physicians in adverse impact of EDCs and PPCPs on humans via drinking
clinical practice, misuse by the public, improper sales water is not conclusive, as a precautionary principle we can
together with crowding and improper sewage disposal say that our drinking water should be free of chemicals that
contribute to the development of antibacterial resistant have the potential to cause hormone disruption. Thus
strains in developing countries (Okeke et al. 1999). Also further research is warranted to study to the occurrence and
political unrest, abject poverty, mass migration and unhy- elimination of EDCs and PPCPs from drinking water. No
gienic environments with a lack of health care facilities single treatment process will be able to remove all
nurture antibiotic resistance in those countries (Kapil 2005). contaminants from water and, therefore, multiple treatment
This has increased the overall medical costs of communities systems would probably be required to achieve water
due to frequent hospitalizations, longer hospital stays and treatment goals (Snyder et al. 2006b). Advanced water
elevated treatment costs. This increase in cost due to treatment technologies will also act as secondary barriers
bacterial resistance is of greater consequence, notably in for drinking water contaminants, such as microorganisms,
the developing countries where the economy is already and might as well remove many other unknown chemicals
overburdened. Resistant genes could very well be trans- that are yet to be reported (Betts 2002; Reynolds 2003).
ported to other areas via watercourses and even through However, the cost of advanced treatment technologies must
migration of people and tourists. be justified before they are implemented.
Industrialized nations, along the pathway of their Due to various socio-economic factors, the risk of
development, have observed a shift in the epidemiological exposure to chemicals causing endocrine disruption is
transition to the suite of chronic illness such as asthma, significantly higher in developing countries. However, little
239 M. F. Rahman et al. | EDCs and PPCPs in the aquatic environment Journal of Water and Health | 07.2 | 2009

has been done towards addressing this issue, partly because and OH radicals: a predictive tool for drinking water
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Adams, C., Asce, M., Wang, Y., Loftin, K. & Meyer, M. 2002
and health-related problems. There is also a significant gap in Removal of antibiotics from surface and distilled water in
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