Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment

Environmental Pollution 158 (2010) 3462e3471

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Review

Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment Kyle E. Murray a, *, Sheeba M. Thomas b, Adria A. Bodour c a

Center for Water Research, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249-0663, USA San Antonio River Authority, San Antonio, TX, USA c Air Force Center for Engineering and the Environment (AFCEE), Brooks City-Base, TX, USA b

Highest priority trace pollutants and ECs include EE2, carbamazepine, bE2, DEET, PFOA, triclosan, diazinon, acetaminophen, PFOS, methoxychlor, E1, and DEHP.

a r t i c l e i n f o

a b s t r a c t

Article history: Received 10 June 2010 Received in revised form 10 August 2010 Accepted 13 August 2010

Organic chemicals have been detected at trace concentrations in the freshwater environment for decades. Though the term trace pollutant indicates low concentrations normally in the nanogram or microgram per liter range, many of these pollutants can exceed an acceptable daily intake (ADI) for humans. Trace pollutants referred to as emerging contaminants (ECs) have recently been detected in the freshwater environment and may have adverse human health effects. Analytical techniques continue to improve; therefore, the number and frequency of detections of ECs are increasing. It is difficult for regulators to restrict use of pollutants that are a human health hazard; scientists to improve treatment techniques for higher priority pollutants; and the public to modify consumption patterns due to the vast number of ECs and the breadth of literature on the occurrence, use, and toxicity. Hence, this paper examines literature containing occurrence and toxicity data for three broad classes of trace pollutants and ECs (industrials, pesticides, and pharmaceuticals and personal care products (PPCPs)), and assesses the relevance of 71 individual compounds. The evaluation indicates that widely used industrials (BPF) and PPCPs (AHTN, HHCB, ibuprofen, and estriol) occur frequently in samples from the freshwater environment but toxicity data were not available; thus, it is important to establish their ADI. Other widely used industrials (BDE-47, BDE-99) and pesticides (benomyl, carbendazim, aldrin, endrin, ethion, malathion, biphenthrin, and cypermethrin) have established ADI values but occurrence in the freshwater environment was not well documented. The highest priority pollutants for regulation and treatment should include industrials (PFOA, PFOS and DEHP), pesticides (diazinon, methoxychlor, and dieldrin), and PPCPs (EE2, carbamazepine, bE2, DEET, triclosan, acetaminophen, and E1) because they occur frequently in the freshwater environment and pose a human health hazard at environmental concentrations. Ó 2010 Elsevier Ltd. All rights reserved.

Keywords: Industrials Pesticides Pharmaceuticals and personal care products (PPCPs) Toxicity Drinking water

1. Introduction A vast number of synthetic organic compounds have been produced for industrial, domestic, or agricultural use. Some portion of the organic compounds used for industrial or domestic purposes will enter wastewater as part of the influent. Unless specifically removed by wastewater treatment processes, they may persist as part of the effluent and be released into receiving waters as trace pollutants (Daughton, 2003; Heberer, 2002b; Lishman et al., 2006). Some fraction of the organic compounds used for agricultural purposes will runoff into a surface water body, while another

* Corresponding author. E-mail address: [email protected] (K.E. Murray). 0269-7491/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2010.08.009

fraction of the compounds will infiltrate and reach the groundwater system. The receiving waters for trace pollutants may be a direct source of drinking water or indirectly reach a water supply as recharge water. Surface water and groundwater are collectively referred to as the freshwater environment in this article and the resource of concern. The term trace pollutant indicates low concentrations of an environmental contaminant normally in the nanogram (ng) or microgram per liter (mg L
1) range. Some trace pollutants are referred to as emerging contaminants (ECs) because they have recently been analyzed and are believed to adversely affect human health or the environment. It is challenging to develop a comprehensive list of compounds labeled as ECs because such a list must be dynamic, as new chemicals are continuously developed and produced. Limited data are available regarding the occurrence of

K.E. Murray et al. / Environmental Pollution 158 (2010) 3462e3471

ECs in the freshwater environment because of the difficulty and expense involved in analysis, and sampling and analysis protocols have focused on regulated compounds. The objective of risk assessment is to establish safe levels of chemical exposure “without appreciable health risk” to humans (Dorne et al., 2007). It is believed that long-term consumption of trace pollutants and ECs can cause adverse health effects in most organisms at concentrations as low as a few ng L
1 (Oros et al., 2003). Trace pollutants and ECs may act as endocrine disrupting compounds (EDCs) (Carlsen et al., 1992; Petrovic et al., 2004); however, predicting the human health effects caused by exposure to ECs is a difficult task (Petrovic et al., 2004). Environmental and health protection agencies establish regulatory levels for ECs in drinking water or permissible levels for ECs in environmental discharges. The U.S. EPA developed a list of 126 priority pollutants (http://www.epa.gov/waterscience/methods/ pollutants.htm) that were to be regulated and monitored, particularly in wastewater effluent, to protect freshwater in the United States. Numerous compounds are on the EPA’s Contaminant Candidate List (CCL), which is a list of unregulated environmental contaminants that are to be monitored. Future regulation of compounds on the CCL are to be based on their occurrence and health effects (Richardson, 2003). The European Union (EU) water framework established environmental quality standards (EQS) for surface water with a list of 33 substances, most of which are organic compounds. The EU directive is intended to help identify causes of pollution and deal with the source of the pollutants (EU, 2008). The U.S. EPA CCL and the EU directive are not designed to prioritize research needs for the compounds based on their known occurrences or toxicity. An analysis of trace pollutant and EC occurrence in the freshwater environment and the corresponding acceptable daily intakes (ADIs) allows us to better prioritize research needs and regulation of chemical use. 2. Objectives and approach The objectives of this paper are to provide an overview of the literature on trace pollutants and ECs in the freshwater environment, tabulate occurrence and human health risk data for the most

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widely reported trace pollutants and ECs, compare the frequency of occurrence and human health risk relative to other trace pollutants and ECs, and prioritize trace pollutant and ECs research needs. 2.1. Occurrence in the freshwater environment Organic compounds have been detected at trace concentrations in the freshwater environment for decades (Barnes et al., 2008; Kolpin et al., 2002b; Loos et al., 2009), and are detectable with current technology. Numerous pharmaceuticals, including carbamazepine, clofibric acid, diclofenac, fenofibric acid, gemfibrozil, and naproxen were ubiquitous in German sewage treatment plant effluent and river waters (Ternes, 1998). Benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE1C) were the most frequently detected persistent organic pollutants in European river waters (Loos et al., 2009). ECs such as coprostanol, N,N-diethyltoluamide (DEET), caffeine, and triclosan were among the most frequently detected organic wastewater contaminants in U.S. streams (Kolpin et al., 2002b). DEET, Bisphenol A (BPA), tri(2-chloroethyl) phosphate, and sulfamethoxazole were among the most frequently detected organic wastewater contaminants in U.S. groundwater (Barnes et al., 2008). It is debatable which compounds occur most frequently since example large-scale sampling programs measured a limited number of analytes; hence, the need to compile data from these programs into a composite dataset. An extensive literature review was conducted for trace pollutants and ECs in surface water (Focazio et al., 2008; Fromme et al., 2002; Gilliom et al., 2006; Kolpin et al., 2002b, 2004; Leong et al., 2007; Loos et al., 2009; Ternes, 1998), groundwater (Focazio et al., 2008; Gilliom et al., 2006; Kolpin et al., 1997), or drinking water (Badach et al., 2000; Snyder et al., 2008). Occurrence data were expressed as frequency of detections and compiled (Tables 1e3) from these studies conducted in North America, Europe, or Asia. Occurrence data from multiple programs were not combined because some reports did not include the number of samples collected. The highest frequency of detection was reported in Tables 1e3 when multiple programs reported occurrence data for the same compound. Maximum and median or mean concentrations were also compiled

Table 1 Widely reported industrial compounds in the freshwater environment. Sub-Group

Common Use

Compound

anti-oxidants

food additive food additive water proofing, protective coatings water proofing, protective coatings surfactant, household surfactant, household constituents of epoxy plastic, fungicide constituents of epoxy plastic, fungicide plasticizer plasticizer

butylated hydroxyanisole (BHA) butylated hydroxytoluene (BHT) perfluorooctanic acid (PFOA)

perfluorates

phenols

phthalates

polybrominated diphenylethers (PBDEs)

cleaners cleaners resins and

perfluorooctanesulfonic acid (PFOS) nonylphenol (NP) tert-octylphenol (OP) bisphenol A (BPA)

resins and

bisphenol F (BPF)

plasticizer flame retardant flame retardant

triazoles

corrosion inhibitors corrosion inhibitors, deicing

*Reference Code listed as footnote to Table 3.

diethyl phthalate (DEP) bis(2-ethylhexyl) phthalate (DEHP) dibutyl phthalate (DBP) 2,20 ,4,40 -Tetrabromodiphenyl Ether (BDE-47) 2,20 ,4,40 ,5-Pentabromodiphenyl ether (BDE-99) benzotriazole (BT) tolyltriazole (TT)

ADI (mg kg
1$day
1)

Detect Freq (%)

Med or Mean Conc (mg L
1)

Max Conc (mg L
1)

Reference Code*

3.0E-01 1.5E-03

6.0 2.4 97.0

5.0E-02 1.0E-01 3.0E-03

5.0E-02 1.0E-01 1.9Eþ01

NA, O, O, O T, I, I, I N, L, L, F

1.5E-04

94.0

6.0E-03

1.4Eþ00

N, L, L, L

5.0E-02 1.5E-01 5.0E-02

50.6 8.0 41.2

8.0E-01 1.3E-02 1.4E-01

4.0Eþ01 5.6E-01 1.2Eþ01

O, I, I, I O, L, L, L S, I, I, I

1.8E-01

NA, E, NA, E

77.0 8.0E-01 2.0E-02

11.1 99.0

2.0E-01 2.2Eþ00

4.2E-01 9.8Eþ01

S, I, I, I S, E, E, E

1.0E-01 4.0E-04

99.0

5.0E-01

8.8Eþ00 1.0E-05

S, E, E, E S, NA, NA, P

6.1E-06

S, NA, NA, P

8.0Eþ00 1.9Eþ01

N, L, L, L N, L, L, L

1.0E-04 3.0E-01 2.5E-01

94.0 81.0

2.3E-01 1.4E-01

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Table 2 Widely reported pesticide compounds in the freshwater environment. Sub-Group

Common Use Compound

carbamates

fungicide insecticide fungicide chloro- acetanilides herbicide herbicide herbicide chlorophenoxy acids herbicide herbicide organochlorines

organophosphates

pyrethroids

triazines

other pesticides

insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide insecticide herbicide herbicide herbicide herbicide herbicide herbicide herbicide

benomyl carbaryl carbendazim acetochlor alachlor metolachlor bentazone 2, 4-dichlorophenoxyacetic acid (2,4-D) aldrin endrin DDT dieldrin endosulfan heptachlor lindane methoxychlor chlorpyrifos diazinon ethion malathion biphenthrin cypermethrin esfenvalerate cyanazine simazine atrazine diuron isoproturon mecoprop (MCPP) prometon

ADI (mg kg
1$day
1) Detect Freq (%) Med or Mean Conc (mg L
1) Max Conc (mg L
1) Reference Code* 5.0E-02 1.0E-01 3.0E-02 2.0E-02 1.0E-02 1.5E-01 3.0E-02 1.0E-02 3.0E-05 3.0E-04 5.0E-04 5.0E-05 6.0E-03 5.0E-04 5.6E-04 2.0E-04 3.0E-03 9.0E-05 5.0E-05 2.0E-02 1.5E-02 1.0E-02 2.0E-02 5.0E-03 3.5E-02 2.0E-03 3.0E-03 1.0E-03 1.5E-02

16.5

4.0E-02

1.0E-01

48.0 7.5 39.2 69.0 52.0

1.0E-01 5.0E-02 1.0Eþ00 4.0E-03 3.0E-03

2.0E-01 6.3E-01 1.1Eþ01 2.5E-01 1.2Eþ00

22.0 4.7 8.0 9.0 24.0 20.0 15.3 25.9

1.8E-01 1.8E-01

2.0E-02 1.0E-01 6.0E-02 7.0E-02

9.0E-01 2.1E-01 1.8Eþ00 2.4E-01 2.0E-01 1.7Eþ00 3.1E-01 1.1Eþ00

17.0

70.0 26.0 68.0 70.0 70.0 43.0 25.7

1.0E-01 1.0E-02 2.0Eþ00 1.0E-02 4.0E-03 1.5E-02

1.4E-01 3.0E-01 1.7E-01 2.1Eþ00 8.6E-01 2.0Eþ00 1.9E-01 1.0Eþ00

S, NA, NA, NA S, I, I, I N, NA, NA, NA S, G, G, G S, H, G, H S, D, G, H S, L, L, L S, L, L, L S, NA, NA, NA S, NA, NA, NA S, A, A, A S, I, I, I S, K, NA, K S, K, NA, K O, A, A, A O, A, A, A S, I, I, I R, I, I, J S, NA, NA, NA S, G, NA, NA S, NA, NA, NA S, NA, NA, NA U, NA, NA, C NA, G, G, H S, L, L, L S, L, G, H S, L, L, L N, L, L, L S, L, L, L S, D, NA, H

*Reference Code listed as footnote to Table 3.

from the same reports. Emphasis was placed on the “worst-case scenario” because maximum concentrations were more commonly reported than median concentrations. This is due to the difficulty in estimating a median when compound concentrations were below the reporting limit of the analytical technique.

generally belong to one of three broad groups 1) industrials, 2) pesticides, or 3) pharmaceuticals and personal care products (PPCPs) (as shown in Tables 1e3). These broad groups are further subdivided by chemical type, and common uses with occurrence and toxicity data provided for specific compounds within each subgroup (Tables 1e3).

2.2. Health risk 3.1. Industrials Various measures of the health hazard posed by a compound are used for regulating their use including ADI and the reference dose (RfD) (Dorne et al., 2007). The ADI and RfD are normally based on oral exposure of fauna to various doses of a compound until a Lowest Observed Adverse Effect Level (LOAEL) is reached. The LOAEL is then divided by an uncertainty factor (e.g., normally 100) to compute an ADI (Galli et al., 2008). The uncertainty factor conservatively compensates for the difference between effects on animal versus human subject. The resulting ADI serves as a reasonable measure of the health risk posed by a compound and allows for comparison of toxicity of compounds relative to one another. ADIs are normally expressed as mass of compound consumed daily per body mass of the individual (mg kg
1$day
1). In this evaluation, the U.S. EPA Integrated Risk Information System (USEPA, 2010) was used as the primary source when compiling ADI values (i.e., RfD values) in Tables 1e3. Additional ADI values were compiled from multiple articles that emphasized human health risk assessment (Blanset et al., 2007; Muñoz et al., 2010; Schriks et al., 2010; Snyder et al., 2008; Teuschler et al., 1999; Walton et al., 1999; WHO, 2002). 3. Groups of trace pollutants and ECs A review of the literature showed that trace pollutants and ECs receiving the most attention by researchers and regulators

Organic chemicals in this group are used in manufacturing and production processes. 3.1.1. Anti-oxidants These compounds are often in cosmetics, pharmaceuticals, rubber and petroleum products, or used to preserve food. Two of the more widely used anti-oxidants, butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) (Thomas et al., 2009), have been shown to be toxic to aquatic organisms (Jos et al., 2005; Sarafian et al., 2002). BHT has been detected in the freshwater environment (Kolpin et al., 2002b). 3.1.2. Perfluorates Perfluorinated compounds are characterized by a hydrophobic alkylated chain saturated with fluorine atoms (Clara et al., 2009). Perfluorates are most commonly used as components of liquid repellents or protective coatings. The water-soluble perfluorinated acids have recently been reported as ECs because they are considered to be persistent organic pollutants (Fromme et al., 2009). 3.1.3. Phenols This group includes bisphenols, and alkylphenols. Bisphenols such as bisphenol A (BPA) and bisphenol F (BPF) are constituents of some epoxy resins and plastics and sometimes used as fungicides

K.E. Murray et al. / Environmental Pollution 158 (2010) 3462e3471

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Table 3 Widely reported pharmaceuticals and personal care products (PPCPs) in the freshwater environment. Sub-Group

Common Use

Compound

ADI (mg kg
1$day
1)

Detect Freq (%)

Med or Mean Conc (mg L
1)

Max Conc (mg L
1)

Reference Code*

analgesics

antipyretic, pain reliever pain reliever anticonvulsant lipid regulator lipid regulator lipid regulator antibiotic antibiotic antibiotic antibiotic antiseptic antibiotic fragrance

acetaminophen

8.3E-04

23.8

1.1E-01

1.0Eþ01

B, I, I, I

acetylsalicylic acid carbamazepine fenofibric acid clofibric acid gemfibrozil erythromycin roxithromycin sulfamethoxazole tetracycline triclosan trimethoprim acetyl-hexamethyltetrahydro-naphthalene (AHTN) hexahydrohexamethylcyclopentabenzopyran (HHCB) diclofenac ibuprofen ketoprofen naproxen estrone (E1) 17a-estradiol (aE2) 17 b-estradiol (bE2) 17 a-ethinyl estradiol (EE2) estriol (E3) acetophenone caffeine N,N-diethyl-metatolumide (DEET)

7.0E-03 3.4E-04

40.0 95.0 60.5 81.4 3.6 21.5 4.8 75.0 1.2 57.6 26.7 36.7

1.6E-01 7.5E-02 4.5E-02 6.6E-02 4.8E-02 6.4E-01 5.0E-02 1.5E-02 1.1E-01 1.4E-01 1.5E-01

3.4E-01 1.2Eþ01 2.8E-01 5.5E-01 7.9E-01 1.7Eþ00 1.8E-01 4.1Eþ00 1.1E-01 2.3Eþ00 7.1E-01 1.2Eþ00

N, Q, Q, Q N, L, L, L NA, Q, Q, Q N, Q, Q, Q O, I, I, I M, I, M, I NA, I, I, I N, L, L, L NA, I, I, I B, I, I, I M, J, I, I NA, J, NA, J

9.7E-01

NA, D, NA, D

anti-epileptic drugs (AEDs) antihyper-lipidemics

antimicrobials

polycyclic musks (PCMs)

fragrance

non-steroidal anti-inflammatory drugs (NSAIDs) synthetic hormones

other PPCPs

anti-inflam-matory anti-inflam-matory anti-inflam-matory anti-inflam-matory hormone hormone hormone hormone hormone fragrance stimulant insect repellant

1.0E-02 1.3E-03 4.0E-02 1.3E-01 1.9E-04 9.4E-03

16.2

6.7E-02

5.7E-01 1.3E-05 5.0E-06 1.0E-07

1.0E-01 8.2E-05

83.0 62.0 14.0 69.0 17.0 5.7 10.6 15.7

1.5E-01 6.0E-03 1.0E-02 4.0E-03 4.0E-03 3.0E-02 1.6E-01 7.3E-02

1.2Eþ00 3.1Eþ01 2.4E-01 2.0Eþ00 1.1E-01 7.4E-02 2.0E-01 8.3E-01

O, L, Q, Q NA, L, L, L NA, L, L, L O, L, L, L O, L, L, I NA, I, I, I O, I, I, I O, I, I, I

21.4 9.4 95.0 74.1

1.9E-02 1.5E-01 9.6E-01 6.0E-02

5.1E-02 4.1E-01 4.0Eþ01 1.1Eþ00

NA, I, I, I S, I, I, I NA, L, L, L B, I, I, I

*NA e Not Applicable; A (Badach et al., 2000); B (Blanset et al., 2007); C (Brady et al., 2006); D (Focazio et al., 2008); E (Fromme et al., 2002); F (Fromme et al., 2009); G (Gilliom et al., 2006); H (Kolpin et al., 1997); I (Kolpin et al., 2002a); J (Kolpin et al., 2004); K (Leong et al., 2007); L (Loos et al., 2009); M (Muñoz et al., 2010); N (Schriks et al., 2010); O (Snyder et al., 2008); P (Streets et al., 2006); Q (Ternes, 1998); R (Teuschler et al., 1999); S (USEPA, 2010); T (Walton et al., 1999); U (WHO, 2002).

(Fromme et al., 2002; Rudel et al., 1998). BPA has the potential to cause reproductive and developmental damages (Mantovani et al., 1999). Alkylphenols are largely used in the manufacture of household and industrial products, such as textiles, metal working fluids, polymeric material production, paper, paints, food, detergents and personal care cosmetic products as emulsifiers or dispersing agents (Liu et al., 2004; Tan et al., 2007). The alkylphenols degrade into 4para-nonylphenol (NP) and para-tert-octylphenol (OP), which are EDCs and detected in wastewater (Gasperi et al., 2008; Ning et al., 2007). 3.1.4. Phthalates These are industrially important chemicals widely used as plasticizers to improve the flexibility of various plastics, paints and synthetic fibers (Zeng et al., 2008). There are approximately 60 different phthalates produced worldwide. Some of the industrially important compounds include diethyl phthalate (DEP), dibutyl phthalate (DBP) and dimethyl phthalate (DMP) (Gültekin and Ince, 2007). Most phthalates have low solubility values and tend to be hydrophobic (Bauer and Herrmann, 1997; Cheng et al., 2008). Since these phthalates are not chemically bonded to the products, they easily leach out and are widespread in aquatic environments (Oliver et al., 2007; Staples et al., 1997). 3.1.5. Polybrominated diphenylethers (PBDEs) PBDEs are used as flame retardants in many consumer and commercial products such as computers, televisions, textiles, furniture, and other building materials (Birnbaum and Staskal, 2004; Qu et al., 2007). These brominated flame retardants are

persistent in the environment, bioaccumulative (Vos et al., 2000), and have the potential for endocrine disruption (Moon et al., 2007). However, PBDEs have a very low solubility and are only detected at the picogram per liter level in the freshwater environment (de Boer et al., 2003; Streets et al., 2006). 3.1.6. Triazoles Benzotriazole (BT) and tolyltriazole (TT) are widely used as anticorrosives in antifreezing products, aircraft deicing agents, and dishwasher detergents (Giger et al., 2006). BT and TT are ubiquitous in surface waters of Europe and Scandanavia (Loos et al., 2009). 3.2. Pesticides A pesticide is a substance used to kill a pest; therefore, various sub-classes of pesticides based on target pests include but are not limited to herbicides, insecticides, and fungicides. Numerous pesticides have the potential to cause endocrine disruption including: 1) insecticides such as chlorpyrifos, chlordane, parathion, lindane, and malathion; 2) herbicides such as diuron, prodiamine, thiazopyr, trifluralin; and 3) fungicides such as vinclozolin, phenylphenol, and carbendazim (McKinlay et al., 2008). Pesticides are generally classified by chemical makeup as carbamates, chloroacetanildes, chlorophenoxy acids, organochlorines, organophosphates, pyrethroids, and triazines (Birkett and Lester, 2003; Hornsby et al., 1996; McKinlay et al., 2008). Studies (Karen et al., 1998; Leong et al., 2007) have shown that organochlorines and organophosphates have the potential to cause adverse effects on biota and humans.

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3.2.1. Carbamates These compounds are effective herbicides, insecticides, and fungicides (Machemer and Pickel, 1994; Sánchez-Brunete et al., 2003), and are highly biodegradable (Fava et al., 2007; Schrijver and Mot, 1999). Carbaryl is one of the most extensively used pesticides (Gilliom et al., 2006) and has been detected in groundwater of the United States (Lindsey et al., 2006). Carbendazim has been found in wastewater influent (Kupper et al., 2006), but occurrence in the freshwater environment has not been documented.

3.2.8. Other pesticides Several other pesticides including diuron, the phenylurea herbicide isoproturon, mecoprop (MCPP), and prometon do not fall within the aforementioned groups. However, they are widely used, occur in the freshwater environment (Barth et al., 2009; Kolpin et al., 1997; Loos et al., 2009), have available toxicological data, and may be more persistent than other pesticides (Gilliom et al., 2006). 3.3. Pharmaceuticals and personal care products (PPCPs)

3.2.2. Chloroacetanilides Chloroacetanilides are generally used as pre-emergent herbicides to control broadleaf and grassy weeds. Metolachlor was one of the most frequently detected pesticides in groundwater and surface water of the United States (Focazio et al., 2008; Kolpin et al., 2002a). Alachlor was also detected in surface water and groundwater in the United States, especially in agricultural regions producing corn (Kolpin et al., 1997). Alachlor concentrations and detection frequencies show decreasing trends because acetochlor began to be used in its place in 1994 (Gilliom et al., 2006). 3.2.3. Chlorophenoxy acids These compounds are commonly used as herbicides for agricultural, forestry and weed control activities and tend to sorb to soil (David et al., 2000; Ding et al., 2000). Common examples include bentazone, 2, 4-dichlorophenoxyacetic acid (2,4-D) and triclopyr (Luque-García and Luque de Castro, 2002). 3.2.4. Organochlorines These compounds contain at least one covalently bonded chlorine atom. They are commonly used as agricultural insecticides, are highly persistent in the environment, hydrophobic, have very low solubilities, and are known for their high toxicities (Nhan et al., 2001). Organochlorines that have high frequencies of occurrence in the freshwater environment include 1,1,1-trichloro-2,2-bis(4chlorophenyl)ethane (DDT), dieldrin, lindane, and methoxychlor (Badach et al., 2000; Leong et al., 2007; Lohmann et al., 2009). 3.2.5. Organophosphates These compounds are commonly used as insecticides because they act as neurotoxins. Considered less persistent and less bioaccumulative than most other classes of pesticides, they have the potential to be more toxic (potent cholinesterase inhibitors) than organochlorines or carbamates (Fytianos et al., 1998; McKinlay et al., 2008; Padrón Sanz et al., 2004) and can exhibit moderate to high hydrophobicity (Watanabe and Grismer, 2001). 3.2.6. Pyrethroids These compounds are commonly used as insecticides, are hydrophobic, and can be persistent in the environment. Pyrethroids have a low toxicity relative to other pesticides (specifically the organochlorines) so have recently been used in place of more toxic pesticides. Biphenthrin, cypermethrin, and esfenvalerate are among the most widely used pyrethroids, with esfenvalerate being detected in surface water runoff (Brady et al., 2006). 3.2.7. Triazines These compounds are heavily used in agricultural areas as selective herbicides. Examples of triazines include atrazine, cyanazine, and simazine (Gilliom et al., 2006), of which atrazine was the most heavily used herbicide in the United States during 1997 (Gianessi and Marcelli, 2000). Both atrazine and simazine are water soluble and persistent (Wauchope et al., 1992), and were detected in surface water of Europe (Loos et al., 2009) and groundwater of the United States (Kolpin et al., 2000; Murray and McCray, 2005).

PPCPs are a diverse group of compounds internally or externally administered to the bodies of humans and domestic animals. Many PPCPs are excreted primarily via feces and urine (Daughton, 2001) after being administered to the body; therefore, these chemicals are components of residential and commercial wastewater. PPCPs frequently detected in the freshwater environment include a variety of analgesics, anticonvulsants, anti-epileptic drugs (AEDs), antimicrobials, lipid regulators, polycyclic musks (PCMs), nonsteroidal anti-inflammatory drugs (NSAIDs), synthetic hormones, and others (Esplugas et al., 2007; Heberer and Stan, 1997; Kolpin et al., 2002a, 2002b; Ternes, 1998). PPCPs can exhibit multixenobiotic resistance, are produced in quantities nearing agrochemicals, and show resistance to microbial degradation; therefore, there are concerns for human health (Smital et al., 2004). 3.3.1. Analgesics Analgesics are used to alleviate pain and often are grouped with NSAIDs because they have mild anti-inflammatory effects. Widely used analgesics such as acetaminophen and acetylsalicylic acid occur in the freshwater environment (Barnes et al., 2008; Kolpin et al., 2002b; Ternes, 1998). 3.3.2. Anti-epileptic drugs (AEDs) Anti-epileptic drugs (AEDs) also are referred to as anticonvulsants and are designed to reduce rapid and excessive firing of neurons of the brain. AEDs such as carbamazepine and primidone have been detected in the freshwater environment and are persistent in groundwater (Drewes et al., 2003; Loos et al., 2009; Ternes, 1998). Carbamazepine was ubiquitous in freshwater bodies and difficult to remove with conventional wastewater treatment processes (Zhang et al., 2008). 3.3.3. Antihyperlipidemics Antihyperlipidemics, commonly used as lipid regulators, are normally prescribed to those that have unhealthy levels of cholesterol and are at risk for coronary heart disease. The effects of a lipid regulator are to reduce low-density lipoproteins and increase high-density lipoproteins. Gemfibrozil, clofibric acid, and fenofibric acid are the most commonly reported lipid regulators and occur in municipal effluent and the water environment (Kolpin et al., 2002b; Ternes, 1998; Zurita et al., 2007). 3.3.4. Antimicrobials Antimicrobials are substances that kill or inhibit the growth of microorganisms including bacteria, fungi, or viruses. Antibiotics are antimicrobials that destroy bacteria within the body. The antibiotic roxithromycin is highly persistent in soil in comparison to other antibiotics (Schlüsener and Bester, 2006) such as erythromycin, oleandomycin, tylosin, salinomycin and tiamulin. Antiseptics are antimicrobials that are applied to living tissue to reduce the possibility of infection. Triclosan, the very commonly used antiseptic, has been shown to be highly hydrophobic and have a low solubility in water (Bester, 2005; Heidler et al., 2006), but yet has been detected in wastewaters and surface waters (Bester, 2005;

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Kolpin et al., 2002b). Other commonly used antiseptics, such as biphenylol and chlorophene, have been detected in influent and effluent from WWTPs (Daughton and Ternes, 1999). 3.3.5. Polycyclic musks (PCMs) Personal care products including shampoos, detergents, hair sprays, cleaning products, and skin treatments often contain polycyclic musks (PCMs) as inexpensive fragrances (Smital et al., 2004). European production of the PCMs 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8hexamethylcyclopenta(g)-2-benzopyrane (HHCB) and 7-acetyl -1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronapthalene (AHTN) far exceeded production of other PCMs (Kupper et al., 2006). HHCB was shown to be highly sorptive to sewage sludge (Thomas et al., 2009) and PCMs are known to bioaccumulate (Daughton and Ternes, 1999; Dsikowitzky et al., 2002; Kannan et al., 2005; Rimkus, 1999; Seinen et al., 1999). HHCB and AHTN have also been detected in drinking water (Focazio et al., 2008) and surface water (Kolpin et al., 2004) of the United States. 3.3.6. Non-steroidal anti-inflammatory drugs (NSAIDs) Non-steroidal anti-inflammatory drugs (NSAIDs) are often used to alleviate pain by counteracting the cyclooxygenase enzyme. NSAIDs such as diclofenac, ibuprofen, ketoprofen, and naproxen have been detected in influent wastewaters and surface waters of Europe (Buser et al., 1998, 1999; Loos et al., 2009; Ternes, 1998). 3.3.7. Synthetic hormones Natural hormones such as insulin and thyroxine are produced in the endocrine glands of animals and regulate development, growth, reproduction, and behavior (Richardson, 2003). Phytohormones, such as isoflavones and lignans, are the equivalent compounds naturally produced by plants to control growth and differentiation of plant tissue. Synthetic hormones have the ability to mimic natural hormones; thus, they are prescribed to regulate bodily functions. Synthetic hormones such as estrone (E1), 17a-estradiol (aE2), 17b-estradiol (bE2), 17a-ethinylestradiol (EE2), and estriol (E3), are some of the major contributors to estrogenic activity and changes in physiological effects on organisms in wastewater effluent receiving waters (Daughton and Ternes, 1999; Kuch and Ballschmiter, 2001). In comparison to these potent hormones, phytohormones are known to be weakly estrogenic (Zava et al., 1997). Sources of estrogens into freshwater include land applications of animal waste, agricultural runoff, and effluent from wastewater treatment plants (Peterson et al., 2000; Shore et al., 1993). 3.3.8. Other PPCPs The fragrance (acetophenone), an insect repellant (N,N-diethylmeta-tolumide (DEET)), and a stimulant (caffeine) are widely used chemicals that do not fit into the aforementioned PPCP groups. They have been detected in the freshwater environment of Europe and the United States (Focazio et al., 2008; Kolpin et al., 2002b; Loos et al., 2009). 4. Synthesis and critical evaluation It is a challenge to evaluate the multitude of organic compounds and breadth of literature on trace pollutants and ECs in the freshwater environment. In this section, information for widely used and reported trace pollutants and ECs are presented in three groups: industrials (Table 1), pesticides (Table 2) and PPCPs (Table 3). The rate of occurrence (frequency of detection) was compiled from the literature along with the highest reported maximum and median or mean concentrations (mg L
1) for surface water, groundwater, or drinking water samples. Toxicity of the compound was also

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compiled from the literature using an ADI (mg kg
1$day
1). The previously reported ADIs were generally formulated from the LOAEL and applied an uncertainty factor of 100 (Snyder et al., 2008). Literature sources for detection frequency, concentrations, and toxicity are provided in Tables 1e3. When a concentration in the freshwater environment was available along with the ADI, then a consumption rate posing health risk (CRPHR) was computed for a 70 kg individual using the following equation:

CRPHR ¼

ADI  70 kg concentration  0:001

where CRPHR is a consumption rate (L$day
1) that represents an exceedance of the ADI and therefore a health risk to a 70 kg individual, ADI is measured in mg kg
1$day
1, concentration is measured in mg L
1, and 0.001 is a unit conversion for mass in numerator versus denominator. The CRPHR was computed for both the maximum and average concentrations of the compound reported in the literature. CRPHR computations are presented in graphical form (Fig. 1) to allow for comparison of the risk posed by maximum and average concentrations in the freshwater environment. Fig. 1 shows the CRPHR at the maximum concentration as a point and, when the median or mean was available, extends an error bar to the CRPHR at the average concentration. 4.1. Prioritize trace pollutants and ECs Trace pollutants and ECs that pose the greatest health hazard have a high occurrence and a low CRPHR. Because the average daily water requirements for humans have been reported to range from 1.8 to 5 L$day
1 (Gleick, 1996), any compounds for which the CRPHR is less than 2 L$day
1 were considered very high priority pollutants. Based on this approach the PPCPs EE2, carbamazepine, and bE2 are very high priority pollutants. Applying an uncertainty factor of 10 to the average daily water requirement (2 L$day
1) sets the next CRPHR threshold at 20 L$day
1. The industrials PFOA, PFOS, and DEHP, pesticides diazinon, methoxychlor, and dieldrin, and PPCPs DEET, triclosan, acetaminophen, and E1 are high priority pollutants with a CRPHR of less than 20 L$day
1 at the maximum concentration compiled from the literature. It is reasonable to include these ten compounds as high priority pollutants because average residential end use of water greatly exceeds the daily water requirement in industrialized nations, sometimes up to hundreds of liters per day (Gleick, 1996). Applying an uncertainty factor of 100 to the average daily water requirement (2 L$day
1) sets the next CRPHR threshold at 200 L$day
1. The industrial NP, pesticides DDT, isoproturon, heptachlor, and diuron, and PPCP gemfibrozil are intermediate priority pollutants with a CRPHR of less than 200 L$day
1 at the maximum concentration compiled from the literature. The remaining compounds, for which we were able to compile an ADI and a maximum concentration in the freshwater environment, are low priority pollutants using this methodology. These compounds are low priority because the CRPHR exceeds 200 L$day
1, indicating a low likelihood of posing a human health hazard at concentrations in the freshwater environment. 4.2. Establish ADI Several compounds examined in this study frequently occur in the freshwater environment, and are believed to pose a health risk; however, the ADI of the compound has not been established. The industrials BHA and BPF, pesticide cyanazine, and PPCPs fenofibric acid, tetracycline, AHTN, HHCB, ibuprofen, ketoprofen, aE2, and E3 must be studied to establish reasonable LOAEL and corresponding

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K.E. Murray et al. / Environmental Pollution 158 (2010) 3462e3471

Fig. 1. Consumption Rate Posing Health Risk at the ADI versus the occurrence of the compound in the freshwater environment.

ADI values. Based on presence in the freshwater environment, it is necessary to establish the toxicity of these compounds and then further prioritize research on trace pollutants and ECs. 4.3. Establish occurrence in the water environment The frequency of occurrence and/or the concentrations of industrials BDE-47 and BDE-99; and pesticides benomyl, carbendazim, aldrin, endrin, ethion, malathion, biphenthrin, cypermethrin, esfenvalerate are not well documented in the literature. Based on potential human health risk, it is important to implement sampling and analytical protocols that document the occurrence and concentrations of these compounds in the freshwater environment. 4.4. Establish ADI and occurrence Several compounds were commonly noted in the ECs literature but could not be evaluated because ADI and occurrence data were unavailable or not comparable. Industrial compounds monobutyltin, dibutyltin, and tributyltin (organotins) have been reported as ECs (Cao et al., 2009; Richardson, 2009), and have primarily been found to occur in marine waters. Compounds occurring in marine waters were not addressed in this article. Other industrials such as dimethyl phthalate (Staples et al., 1997) and hexabromocyclododecane (Birnbaum and Staskal, 2004) are recently reported ECs, but should be further studied to establish ADI values and occurrence. Pesticides such as parathion (McKinlay et al., 2008) and triclopyr (Luque-García and Luque de Castro, 2002) are mentioned in the literature, but ADI values and occurrence in the freshwater environment was not well documented. PPCPs commonly used as UV protectants (benzophenones BP2 and BP3) were reported as being persistent in the environment, having the potential to bioaccumulate, and exerting uterotropic effects by binding to estrogen receptors (Kunz and Fent,

2006; Schlecht et al., 2004). The anticonvulsant primidone (Heberer, 2002a) is also noted in the literature, again an ADI value or occurrence data are not well reported.

5. Conclusions Because of the vast number of trace pollutants and ECs and the breadth of literature on the occurrence, use, and toxicity it is difficult for regulators to evaluate pollutants that pose the greatest risk to human health; scientists to improve treatment techniques for higher priority pollutants; and the public to modify consumption patterns. Many trace pollutants and ECs are not considered priority pollutants of concern because they are not analyzed in standard water sampling protocols, they are below detection limits of existing analytical techniques, their occurrence in the freshwater environment is not well documented, or their toxicity is not established. Seventy-one compounds within three broad classes of chemicals (industrials, pesticides, and PPCPs) were examined in this study to assess the relative risk to human health posed by each trace pollutant and EC. Several widely used industrials (such as BPF) and PPCPs (such as AHTN, HHCB, ibuprofen, and estriol) occur frequently in samples from the freshwater environment but toxicity data were not available; thus, it is important to establish ADIs for these compounds. Other widely used industrials (BDE-47, BDE-99) and pesticides (benomyl, carbendazim, aldrin, endrin, ethion, malathion, biphenthrin, and cypermethrin) have established ADI values but their occurrence in the was not well documented; therefore, it is important to include these compounds in freshwater sampling programs. The highest priority pollutants for regulation and treatment should include industrials (PFOA, PFOS, DEHP), pesticides (diazinon, methoxychlor, and dieldrin), and PPCPs (EE2, carbamazepine, bE2, DEET, triclosan, acetaminophen, and E1) because they frequently occur in the freshwater

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