Occurrence of Perfluorinated Compounds in Raw Water from New

Nov 4, 2013 - Office of Science, New Jersey Department of Environmental Protection, Mail Code 428-01, P.O. Box 420, Trenton, New Jersey 08625, United ...
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Occurrence of Perfluorinated Compounds in Raw Water from New Jersey Public Drinking Water Systems Gloria B. Post,* Judith B. Louis, R. Lee Lippincott, and Nicholas A. Procopio Office of Science, New Jersey Department of Environmental Protection, Mail Code 428-01, P.O. Box 420, Trenton, New Jersey 08625, United States S Supporting Information *

ABSTRACT: Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were previously detected (≥4 ng/L) in 65% and 30%, respectively, of 23 New Jersey (NJ) public drinking water systems (PWS) sampled in 2006. We now report on a 2009 study of the occurrence of PFOA, PFOS, and eight other perfluorinated compounds (PFCs) in raw water samples from 30 intakes (18 groundwater and 12 surface water) from 29 additional NJ PWS. Between 1 and 8 PFCs were detected (≥5 ng/L) in 21 (70%) of 30 PWS samples at total PFC concentrations of 5−174 ng/L. Although PFOA was the most commonly detected PFC (57% of samples) and was found at the highest maximum concentration (100 ng/L), some of the higher levels of other PFCs were at sites with little or no PFOA. Perfluorononanoic acid was detected more frequently (30%) and at higher concentrations (up to 96 ng/L) than in raw or finished drinking water elsewhere, and it was found at several sites as the sole or predominant PFC, a pattern not reported in other drinking water studies. PFOS, perfluoropentanoic acid, and perfluorohexanoic acid were each detected in more than 20% of samples, while perfluoroheptanoic acid, perfluorobutane sulfonic acid, and perfluorohexane sulfonic acid were detected less frequently. Perfluorobutanoic acid was found only once (6 ng/L), and perfluorodecanoic acid was not detected. Total PFCs were highest in two reservoirs near an airfield; these were also the only sites with total perfluorosulfonic acids higher than total perfluorocarboxylic acids (PFCAs). PFC levels in raw and finished water from the same source were similar at those sites where both were tested. Five wells of two additional NJ PWS known to be contaminated with PFOA were also each sampled 4−9 times in 2010−13 for nine of the same PFCs. Total PFCs (almost completely PFCAs) at one of these PWS located near an industrial source of PFCs were higher than in any other PWS tested (up to 330 ng/L). These results show that multiple PFCs are commonly found in raw water from NJ PWS. Future work is needed to develop approaches for assessing the potential human health risks of exposure to mixtures of PFCs found in drinking water and other environmental media.

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INTRODUCTION Perfluorinated chemicals (PFCs) are a class of anthropogenic chemicals found in environmental media worldwide, including finished drinking water, surface water, groundwater, air, sludge, soils, sediments, outdoor and indoor dust, biota, and the polar ice caps.1−3 Their structure consists of a totally fluorinated carbon chain of varying length and a charged functional group, such as carboxylic or sulfonic acid.2 PFCs have been produced for over 60 years.2 Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were previously made and used in the largest amounts, and they are the most intensively studied PFCs thus far.2,4 U.S. production of PFOS and perfluorohexane sulfonic acid (PFHxS) by their major manufacturer ended in 2002,5 while the worldwide use of PFOA and longer chain PFCA homologues, including perfluorononanoic acid (PFNA), is currently being phased out by their major manufacturers.2,6 Due to the phase-outs of these biologically persistent PFCs, shorter chain length PFCs that are generally more rapidly eliminated in humans and animals are increasingly used as alternatives.7 Recent research © 2013 American Chemical Society

has focused on the environmental occurrence, human exposure, and potential health effects of PFCs other than PFOA and PFOS and on mixtures of PFCs in the environment. PFCs repel both oil and water, resist degradation at high temperatures, and are chemically inert. These properties make them useful in commercial products including water-, soil-, oil-, and stain-resistant coatings for consumer products, aviation hydraulic fluids, fire-fighting foams, paints, adhesives, waxes, polishes, and other products; industrially as surfactants, emulsifiers, wetting agents, additives, and coatings; and as processing aids (emulsifiers) in the production of fluoropolymers and fluoroelastomers.3,4,8 Because of the extreme stability of their carbon−fluorine bonds,8 PFCs are highly persistent in the environment.2 PFCs are highly water-soluble in comparison with other well-studied Received: Revised: Accepted: Published: 13266

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other PFCs to reach groundwater through this pathway has not yet been evaluated. In addition to industrial releases, sources of PFCs in groundwater or surface water include discharge from wastewater treatment plants treating domestic and/or industrial waste, street- and stormwater runoff, release of aqueous firefighting foams, and land application of biosolids or contaminated industrial waste.3 Another source of PFCs in the environment is the biodegradation in soil, sludge, and wastewater of precursor compounds such as fluorotelomer alcohols (FTOH) and perfluoroalkane sulfonamidoethanols (FOSE) used industrially and in consumer products.8,32−34 Most studies of the occurrence of PFCs in raw or finished drinking water have focused on a limited number of sites from a large geographical area21,35,36 or on sites known or suspected to be contaminated.24,26 Statewide (other than in NJ) surveys have not yet been conducted in the U.S., and only a few fairly comprehensive national or regional surveys have been reported, including nationally in raw water in France37 and tap water in South Korea38 and regionally in tap water in Catalonia, Spain39 and Hesse, Germany.40 After detection of PFOA in two NJ PWS wells near an industrial source, a statewide study of the occurrence of PFOA and PFOS in NJ PWS was conducted in 2006.20,41 This study included both PWS intended to represent NJ geographically and others selected for their potential vulnerability to PFC and/ or synthetic organic chemical contamination. PFOA and PFOS were detected (≥4 ng/L) in 65% and 30%, respectively, of the 23 PWS tested, and PFC levels were similar in raw and finished water at sites where both were tested. To evaluate the occurrence of additional PFCs and more PWS, we report here on a more recent study of the occurrence of PFOA, PFOS, and 8 other PFCs in 30 intakes of 29 additional NJ PWS. We also report on monitoring data for 9 of these PFCs in raw groundwater from two additional NJ PWS that have taken measures to address PFC contamination.

persistent and bioaccumulative organic pollutants such as polychlorinated dioxins and PCBs that have low water solubilities.3 PFCs cause hepatic, developmental, immune, neurobehavioral, endocrine, and metabolic toxicity in experimental animals, with similarities and differences in toxicological effects and varying potencies among the individual compounds.1 Human exposure to biologically persistent PFCs is associated with numerous health effects in the general population, communities with contaminated drinking water, and/or exposed workers.3,4,9,10 Chronic exposure to PFOA and PFOS caused tumors in experimental animals, but there are no chronic toxicology data for other PFCs.1,4 PFOA was described as a likely human carcinogen by the USEPA Science Advisory Board11 and was linked to two types of cancer in communities with drinking water exposure.12 Four PFCs (PFOA, PFOS, PFNA, PFHxS) were detected in the serum of greater than 99% of a representative sample of the U.S. population13 and are also ubiquitous in the serum of populations worldwide.14 PFOA, PFOS, and PFHxS persist in humans with half-lives of 3−8.5 years, while perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS) have much shorter human half-lives (2−4 days and 10−20 days, respectively).1 The human half-lives of other commonly detected PFCs are unknown, including PFNA, which is more persistent than PFOA in laboratory animals15 and for which human serum levels have increased in recent years.13 PFCs are present in human breast milk and umbilical cord blood, and serum levels in infants and children are generally higher than in adults.1,3 These prenatal and early life exposures are relevant to potential developmental effects.1,3 Sources of human exposure to PFCs include drinking water, food, food packaging, treated carpets, upholstery, and clothing, house dust, protective sprays and waxes, and indoor and outdoor air.1,3 In contrast to other persistent and bioaccumulative organic compounds that are not water-soluble, drinking water can be an important source of human exposure to PFCs. Elevated serum levels of some PFCs have been found in communities with contaminated private wells16−18 and/or public water supplies (PWS).17−20 Ongoing exposure to even relatively low drinking water concentrations of biologically persistent PFCs substantially increases total human exposure. For example, continued drinking water exposure increases PFOA serum levels with a serum/drinking water ratio of approximately 100:1.3,20 PFCs have been found in raw and finished public drinking water from both ground and surface water sources in the U.S. and worldwide.6,21,22 Available information indicates that standard drinking water treatment processes such as coagulation/flocculation, sand filtration, sedimentation, mediumpressure ozonation, chloramination, and chlorination do not effectively remove PFCs, but they can be removed by granular activated carbon (GAC).3,23 PFCs occur in drinking water impacted by discharges from industrial facilities or other known sources of contamination24−26 and also where the source is unknown.20,21 They were detected at high frequency in several river basins that are drinking water sources.27−30 Like other groundwater contaminants, PFCs can reach drinking water wells via the well-established pathway of migration of a groundwater plume. PFOA can also contaminate drinking water wells up to several miles from a source of air emissions from industrial facilities, by deposition from air onto soil and migration through the soil to groundwater.31 The potential for

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METHODS Sampling Sites. Raw water samples were collected between August 2009 and February 2010 from 30 intakes (12 surface water and 18 groundwater) at 29 NJ PWS chosen to represent NJ geographically. Seventeen groundwater samples were from unconfined wells (in the upper unconfined aquifer), and one was from a confined well (sunk into an aquifer located between two impermeable strata). Sources of surface water were rivers (six sites) and reservoirs (six sites). Sampling Procedure. Samples were collected by NJDEP personnel from designated raw water sample taps used for other raw water sampling under N.J.A.C. 7:10-1 et. seq. All sampling procedures complied with N.J.A.C. 7:18-1 et seq., 40 CFR 141. Samples were collected in polyethylene bottles with polypropylene screw caps provided by MWH Laboratories (Monrovia, CA), consistent with the laboratory’s standard operating procedure. Samples were packed in coolers with ice upon collection and shipped overnight to MWH Laboratories. Sampling personnel avoided contact with substances containing fluorochemicals. Nine field blanks were prepared at sampling locations throughout the state to ensure that PFCs were not introduced as a result of background contamination. A field blank was prepared by pouring distilled water into collection bottles on each day that samples were collected, handled in the same 13267

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Figure 1. Locations and total PFC concentrations for NJ PWS sampled for PFCs. Sites 1−30 were sampled for 10 PFCs in 2009−10. PWS-A and PWS-B were monitored for the same PFCs (except PFBA) in 2010−13. The MRL for all PFCs was 5 ng/L. Full names of counties abbreviated here are found in Table S2 (Supporting Information). Developed land represents residential, commercial, and industrial areas and associated infrastructure as mapped by NJDEP.43

liquid chromatography/mass spectrometry in tandem (LC-MS/ MS). The minimum reporting level (MRL) for all 10 PFCs was 5 ng/L. Quality Assurance. Quality assurance (QA) procedures used in the analysis are discussed in detail in MWH SOPHPLC12, Rev. 4.0. These include analysis of a five point calibration curve for each batch of samples, continued calibration verification after 10 or less samples, laboratory reagent blank and MRL (5 ng/L) samples with each batch of samples, and a laboratory fortified blank sample and duplicate sets of laboratory fortified matrix samples for every 20 or less samples. As specified in the method, all calibration curves had a

manner as other samples, and sent to MWH Laboratories for analysis. Analytical Method. Samples and field blanks were analyzed by MWH Laboratories using method MWH SOPHPLC 12, Rev 4.0 that is certified by NJDEP Office of Quality Assurance.42 The samples were analyzed for seven perfluorocarboxylic acids (PFCAs): PFBA, perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), PFOA, PFNA, and perfluorodecanoic acid (PFDA); and three perfluorinated sulfonic acids (PFSAs): PFOS, PFBS, and PFHxS (Table S1, Supporting Information) using solid-phase extraction coupled with high-performance 13268

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r2 value greater than 0.99, a MRL of 5 ng/L, and laboratory fortified blank samples within 100 ± 30% of target values. No PFCs were quantified in eight field blanks, and one field blank contained 59 ng/L PFNA. However, no sample collected on the same date as that field blank contained a reportable amount of PFNA. Data from Two Additional PWS. Data for groundwater from two additional NJ PWS that were monitored for PFCs in 2010−13 were submitted to NJDEP. These samples were analyzed by the same laboratory using the same method as in the primary study. Because the laboratory indicated that the MRL for PFBA was inconsistent for these samples, the data for low levels of PFBA found in some samples is not presented.

the 12 sites at total concentrations of 9−174 ng/L (Figure 3; Table S2, Supporting Information). The six sites with total PFCs of greater than 100 ng/L were all located in the southern half of the state. Regional land-use patterns surrounding the monitoring sites were evaluated to determine the level of association with total PFC concentrations. The percentage of land-uses,43 including developed lands, water, wetlands, forests, agriculture, or barren lands, within 0.6 miles (1 km) of each site are shown in Table S3 (Supporting Information). On the basis of correlation analysis and logistic regression, patterns between total PFC concentration and regional developed land are not evident. PFOA was the most commonly detected compound (57% overall) and was found in 33% of groundwater (≤31 ng/L) and 92% of surface water (≤100 ng/L) samples (Table 1). PFOS was detected in 30% of all samples, with comparable frequency in groundwater (≤12 ng/L) and surface water (≤43 ng/L, Table 1). These results are similar to the 2006 NJ study in which PFOA and PFOS were detected in 65% and 30%, respectively, of 23 PWS.20,41 PFPeA, PFHxA, and PFNA were also detected in greater than 20% of all samples, with similar frequencies in surface water and groundwater (Table 1). Three other compounds, PFHpA, PFBS, and PFHxS, were detected less frequently (10−13%). PFBA was found at a low concentration (6 ng/L) in only one groundwater sample, and PFDA was not detected (Table 1). PFOA (100 ng/L) was highest at site 29, which uses the Metedeconk River as its surface water source (Figure 3; Table S2, Supporting Information). Two other PFCAs were detected at low levels (≤12 ng/L), and PFSAs were not found. The source(s) of the elevated PFOA at site 29 are under investigation and may include a small industrial park located near the PWS intake. PFOA concentrations at other sites were much lower (≤33 ng/L). Samples from two Atlantic County (southern NJ) reservoirs near a civil-military airport (sites 19 and 20) contained numerous PFCs (7 and 8, of the 10 analyzed). They had the highest total concentrations of PFCs (143 and 174 ng/L), PFOS (25−43 ng/L), and PFHxS (44−46 ng/L) and were the only sites at which the three PFSAs analyzed contributed more than 50% of total PFCs. In comparison, the highest levels of PFOS at other sites in this study and in the 2006 NJ study were 12 and 19 ng/L, respectively.41 All of the PFCs found at these sites are found in aqueous firefighting foams (AFFFs) and/or are formed from precursors present in AFFFs.44 Contamination of groundwater and surface water near military and civil airports from use of AFFFs has been reported at other locations.44,45 The PFPeA concentration at groundwater site 15 (74 ng/L) was much higher than the other seven detections of this compound (≤15 ng/L). No other PFCs were detected in this sample, and the source of PFPeA is unknown. PFNA levels (72−96 ng/L) in three NJ PWS (site 5, site 11, and PWS-B) exceeded the highest raw or finished drinking water concentrations reported elsewhere in the literature that we reviewed (58 ng/L, see below). At these three sites, PFNA was the sole or predominant PFC, while PFNA was a minor component of a mixture of PFCs when it was reported in drinking water elsewhere. PFNA (80 ng/L) was the only PFC found at groundwater site 11 in northern NJ and was also the only or the predominant PFC in four other PWS (groundwater site 12 and surface water sites 23, 27, and 28) within 13 miles north of

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RESULTS AND DISCUSSION 2009 Study of PFCs in Raw Water from NJ PWS. Thirty PWS intakes, representing 19 of the 21 counties in NJ, were sampled (Figure 1). One or more PFC was detected (≥5 ng/L) at 21 sites (70%), with the number of individual compounds detected varying from one (8 samples) to a maximum of 8 in one sample (Figures 2 and 3; Table S2, Supporting

Figure 2. PFCs (≥5 ng/L) in raw groundwater samples from NJ PWS. Numbers on x axis refer to sites shown in Figure 1 and Table S2 (Supporting Information). PFCs were not detected at sites 3, 4, 7, 9, 13, 14, 16, and 18.

Figure 3. PFCs (≥5 ng/L) in raw surface water samples from NJ PWS. Numbers on x axis refer to sites shown in Figure 1 and Table S2 (Supporting Information). PFCs were not detected at site 21.

Information). PFCs were detected in 10 of 17 unconfined wells at total concentrations of 5−132 ng/L but not in the only confined well sampled (Figure 2; Table S2, Supporting Information). In surface water, PFCs were detected at 11 of 13269

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Table 1. Detection Frequencies and Concentration Ranges of PFCs in Raw Water from NJ PWSa all sites (n = 30)

groundwater sites (n = 18)

detection

a

surface water sites (n = 12)

detection

detection

PFC

no.

percent

range (ng/L)

no.

percent

range (ng/L)

no.

percent

range (ng/L)

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFBS PFHxS PFOS

1 8 7 4 17 9 0 3 4 9

3% 27% 23% 13% 57% 30% 0% 10% 13% 30%

ND−6 ND−74 ND−17 ND−10 ND−100 ND−96 ND ND−6 ND−46 ND−43

1 4 4 1 6 5 0 1 2 5

6% 22% 22% 6% 33% 28% 0% 6% 11% 28%

ND−6 ND−74 ND−12 ND−5 ND−31 ND−96 ND ND−6 ND−10 ND−12

0 4 3 3 11 4 0 2 2 4

0% 33% 25% 25% 92% 33% 0% 17% 17% 33%

ND ND−15 ND−17 ND−10 ND−100 ND−19 ND ND−6 ND−46 ND−43

MRL for all PFCs was 5 ng/L. ND = not detected.

installed, and PFCs are not detected in finished water (data not shown). At PWS-A, installation of carbon filtration is in progress, and exposure to PFCs is being reduced by blending with water from uncontaminated wells until treatment is in place. Concentrations of individual and total PFCAs in these wells (Table S4, Supporting Information) did not follow an increasing or decreasing trend over time (data not shown). At PWS-A, PFOA (up to 190 ng/L) was previously reported in raw water from shallow unconfined wells in two wellfields a few miles from a facility that used PFOA industrially and processed waste containing PFOA.20 PFPeA, PFHxA, PFHpA, and PFOA were found in all 27 samples from four PWS-A wells, with PFOA contributing 19−48% of the total PFCAs (Table S4, Supporting Information). The highest concentrations of each of these compounds, and total PFCA concentrations (up to 210−330 ng/L), in these PWS-A wells exceeded those found at the 30 sites in the primary study (Figure 4; Table S4, Supporting Information). PFNA was detected in 13 of the 27 samples, at much lower concentrations than the other PFCAs (≤16 ng/L). PFOS was detected in 10 of 27 samples (≤9 ng/L), and PFHxS was detected in 1 of 27 samples (6 ng/L). A possible source of PFC contamination in these wells is the air emission → soil deposition → migration to

site 11 but was not detected at site 10 (groundwater) or site 22 (surface water) within 7 miles south. The highest PFNA level in the study (96 ng/L) was at groundwater site 5 in southern NJ. At this site, PFOA (26 ng/ L) was the only other PFCA detected, at a much lower concentration than PFNA, with PFOS and PFHxS at less than 10 ng/L. PFNA was also detected at up to 72 ng/L in PWS-B (an additional PWS sampled in 2011−12, see below), located about 8 miles southwest of site 5. An industrial facility where large quantities of PFNA were previously used is located near the Delaware River about 2 miles from Site 546,47 and is a possible source of the PFNA groundwater contamination at these two PWS. In 2007−09, PFNA was also found in Delaware River water at up to 976 ng/L starting near the discharge location of this facility and downstream;48 this is higher than the surface water concentrations reported in our literature search of studies elsewhere in the U.S. and worldwide. Elevated levels of perfluoroundecanoic acid (PFUnDA, C11), another PFC used at the facility, were also found in the Delaware River at these same locations;48 PFNA and PFUnDA were also elevated in fish from the same Delaware River locations in 2004−2007.49 PFUnDA was not analyzed in the 2009 study, and it was not detected in raw or finished water at greater than or equal to 2.5 ng/L in recent sampling of site 5 (data not shown). The use of PFNA as a processing aid in fluoropolymer manufacture at this facility46 was similar in nature to the use of PFOA at a West Virginia fluoropolymer manufacturing facility where PFOA emissions to air and water caused regional groundwater contamination.50 To our knowledge, the potential for industrial emissions of PFNA to contaminate groundwater in this manner has not been previously investigated. Although PFOA was by far the most frequently detected PFC (57% of samples), the data suggest that its presence or absence is not necessarily a good indicator of the occurrence of other PFCs in the same water source. For example, the PFPeA was highest at a site where PFOA was not detected, and the two highest levels of PFNA were at sites where PFOA was not detected or was much lower than PFNA. PFCs in Raw Water from Additional NJ PWS. Two PWS (Figure 1; PWS-A, PWS-B) with groundwater known to be contaminated by PFOA were monitored in 2010−13 for 9 of the 10 PFCs analyzed in the primary study. At PWS-B, PFC levels in raw and finished water were similar before the installation of carbon filtration. Carbon filtration has now been

Figure 4. PFCs (≥5 ng/L) in raw groundwater samples from two additional NJ PWS. Multiple samples were taken from each well in 2010−2013 (Table S4, Supporting Information). Data shown are for samples with highest total PFCs from each well. 13270

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Table 2. Detection Frequencies (%) and Maximum Concentrations (ng/L) for PFCs in Raw Drinking Water from NJ and France and Tap Water from Catalonia, Spaina NJ raw water (this study) (n = 30) (≥5 ng/L)

a

France (national) raw water37 (n = 331) (≥4 ng/L)

Catalonia, Spain, tap water39 (n = 40) (≥5 ng/ L)

PFC

detection (%)

maximum (ng/L)

detection (%)

maximum (ng/L)

detection (%)

maximum (ng/L)

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFBS PFHxS PFOS

3% 27% 23% 13% 57% 30% 0% 10% 13% 30%

6 74 17 10 100 96 ND 6 46 43

1% 2% 8% 1% 11% 3% 0% 3% 13% 25%

12 40 139 39 16 52 ND 9 32 62

NA NA 10% x 15% 20% 13% 3% 15% 3% 10%

NA NA 9 18 57 58 10 69 5 58

NA = not analyzed. ND = not detected.

studies of the occurrence of PFCs in raw or finished drinking water have yet been reported. Nationwide monitoring of finished water for six PFCs (PFHpA, PFOA, PFNA, PFBS, PFHxS, and PFOS) will be conducted in 2013−2015 by all PWS serving more than 10 000 people and 800 representative PWS serving less than 10 000 people under the USEPA Unregulated Contaminant Monitoring Rule 3 (UCMR3).51 The MRLs for UCMR3 monitoring of the six PFCs are 10−90 ng/L, higher than the MRL of 5 ng/L achieved by the commercial laboratory in our study, and detections below the UCMR3 MRLs from laboratories that can achieve lower MRLs will not be included in the UCMR3 data set . Raw and finished water from six drinking water utilities located throughout the U.S. that were impacted by wastewater to varying degrees were tested for seven PFCs.35 Of the six PFCs also analyzed in the NJ study, four (PFOA, PFNA, PFHxS, and PFOS) were found at higher maximum concentrations in NJ PWS. Several studies of occurrence of PFCs in raw or finished water have been conducted in other nations. Differences in the profiles of PFCs in drinking water samples from various locations may reflect local differences in industrial and commercial uses of PFCs. Table 2 compares the results of the 2009 NJ study with a comprehensive national study of French raw drinking water from 135 surface water and 196 groundwater sites37 and a regional study of 40 tap water samples from Catalonia, Spain.39 These are the two studies most comparable to the 2009 NJ study, based on suite of compounds evaluated and MRLs. In France, the total concentration of the same 10 PFCs evaluated in NJ was greater than 100 ng/L (156 ng/L) in only one of 331 raw water sources tested. In comparison, the total PFC concentration exceeded 100 ng/L (up to 174 ng/L) at 4 of 30 NJ sites. The three PFSAs analyzed were found at generally comparable frequencies and maximum levels in the French and NJ studies, although PFBS at low levels was found more frequently in NJ. PFOS was found less frequently in Catalonia than in the other two studies, and the maximum concentration of PFBS was much higher there. As in NJ, PFDA was not found in France, but it was found infrequently in Catalonia. Low levels of PFBA were found only in a few groundwater samples in France and NJ, and it was not analyzed in Catalonia. The other five PFCAs (PFPeA, PFHxA, PFHpA, PFOA, and PFNA) were found much more often in NJ than in France, and this was also the case when PFHxA, PFOA, and PFNA detections in NJ are

groundwater pathway described for PFOA.31 To our knowledge, this pathway has not been evaluated for other PFCs. PFOA was detected at greater than 40−610 ng/L in 57% of 109 private wells tested within a 2 mile radius of the industrial facility near PWS-A,3,47 but no data on other PFCs in these private wells are available. In contrast, PFNA was detected at similar concentrations as PFOA in eight samples of a well from PWS-B, with generally lower levels of the three shorter chain PFCAs (PFPeA, PFHpA, and PFHxA) (Figure 4; Table S4, Supporting Information). The highest levels of PFOA, PFNA, and total PFCAs at PWS-B were 60, 72, and 161 ng/L, respectively. PWS-B is about 6 miles northeast of PWS-A and about 8 miles southwest of site 5 where the highest level of PFNA (96 ng/L) was found. Additional Data on PFCs in Raw versus Finished Water at Some PWS Sampled in 2006 and 2009 NJDEP Studies. GAC is not used at any of the PWS in the 2009 study, and available information indicates that the conventional treatment processes in place at these PWS are unlikely to effectively remove PFCs.3,23 In the 2006 NJDEP study of PFOA in NJ PWS, there was no apparent difference in PFOA concentrations when raw and finished water were collected at the same site.20 Several PWS included in the 2006 and 2009 NJDEP studies conducted additional sampling for either PFOA and PFOS, or a larger suite of PFCs, in raw and finished water (Tables S5 and S6, Supporting Information). When data for raw and finished water from the same source are compared, it is evident that PFC concentrations were generally not decreased in the finished water. Finished water at two surface water sites in the 2009 study (sites 19 and 29) is a blend of surface water and groundwater. At site 29, PFOA in raw groundwater was lower than in raw surface water, and the concentration in the blended finished water was intermediate (Table S6, Supporting Information). In finished water at site 19, some PFCs were higher and some lower than in the surface water source, presumably reflecting the concentrations in the groundwater source, which was not tested (Table S5, Supporting Information). Comparisons to Other Studies of PFC Occurrence in Raw and Finished Drinking Water. When comparing PFC concentrations in the NJ raw water samples to concentrations reported raw and finished drinking water from other locations, it should be noted that some finished water data reported in the literature may have been from facilities using treatment that removes PFCs. In the U.S., no other statewide or regional 13271

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Of the PFCs detected in this study, PFOA, PFNA, PFOS, and PFHxS are the four compounds known1 or expected to be most bioaccumulative in humans. They are found in the serum of virtually all U.S. residents.13 Serum levels of PFOA,18−20 PFOS,19 and PFHxS19 were elevated in communities with drinking water contaminated by these compounds, while serum levels have not been evaluated in communities with drinking water contaminated by PFNA. The PFOA concentrations in the surface water source of one PWS in the main study (100 ng/L) and the groundwater sources of the two additional PWS monitored in 2010−13 (up to 91 ng/L) exceeded the NJ health-based guidance of 40 ng/ L.20,41 This guidance was developed prior to the availability of data on developmental toxicity in mice and associations with health effects in the general population and communities with drinking water exposure.3 All of these PWS have taken measures to reduce PFOA in finished water by blending with other water sources or installing GAC. Although its human half-life is unknown, PFNA is excreted more slowly than PFOA in rats and mice,15 suggesting that it may also be more persistent than PFOA in humans. The available data indicate that its effects and mode of action are generally similar to those of PFOA but that it is more potent.54−60 Although no health-based drinking water value has been developed for PFNA, this information suggests that use of a health-based level for PFOA as a preliminary screening benchmark is not overly conservative. In the 2009 study, PFNA levels in raw water from three NJ PWS exceeded the NJ PFOA guidance value (40 ng/L). In recent samples from the well with the highest level (96 ng/L) in the 2009 study, PFNA had increased to 140 ng/L in the raw water and 150 ng/L in finished water (Table S5, Supporting Information). PFOS was detected at up to 43 ng/L in a reservoir in the 2009 study and up to 61 ng/L in raw surface water and 34 ng/L in finished water (blend of surface and groundwater) in recent samples from this PWS (Table S5, Supporting Information). USEPA has developed a Provisional Drinking Water Health Advisory, 200 ng/L, for PFOS that is applicable to short-term exposures.61 It is based on effects in a subchronic monkey study62 in which PFOS serum levels were still increasing linearly when exposure ended at 6 months, suggesting higher internal doses would result from chronic exposures. No healthbased benchmark considered applicable to the evaluation of chronic drinking water exposure to PFOS is available. No health-based drinking water benchmark is available for PFHxS, which was detected at up to 46 ng/L in a reservoir in the 2009 study and up to 54 ng/L in finished water (blend of surface and groundwater) in recent samples from this PWS (Table S5, Supporting Information). Its human half-life, 8.5 years, is the longest known for any PFC,1 and toxicology data are limited. In a rat study of less than subchronic duration that also evaluated reproductive and developmental effects, effects occurred in males at the lowest dose (0.3 mg/kg/day), but no effects were reported in dosed female rats or their offspring even at the highest dose (10 mg/kg/day).5 PFHxS is excreted rapidly in female rats, as is also the case for PFOA and PFNA1 but is retained in both sexes of mice, monkeys, and humans.63 Thus, as for PFOA and PFNA,1 the rat may not be a suitable model for evaluating PHxS developmental effects or general toxicity in females. Like PFOA and PFOS, a single neonatal exposure to PFHxS in mice affected brain development and caused neurobehavioral effects in adulthood.64,65

compared to Catalonia. For PFHxA and PFHpA, maximum concentrations were highest in France, while the highest maximum levels of PFPeA, PFOA, and PFNA were detected in NJ. Comparison of the occurrence frequencies in the NJ study with those reported in some other occurrence studies of finished water is complicated because the data in other studies is reported based on much lower MRLs, method detection limits, or limits of quantitation than the 5 ng/L achieved in our study and because the studies may not indicate whether treatment to remove PFCs was in place. PFOS and six of the PFCAs analyzed in NJ were measured in six tap water samples from the Lake Maggiore, Italy, region; only PFOS was found at greater than 5 ng/L, with a maximum of 9.7 ng/L.52 In 26 tap water samples from Germany (all but two from Hesse) analyzed for the same suite of PFCs measured in NJ, only 5 were detected above 5 ng/L, and the highest concentration of any individual compound was 12 ng/L for PFHxS.40 Ten PFCs (eight of which were analyzed in the NJ study) were measured in 15 tap water samples from eight cities throughout South Korea.38 The maximum total PFC concentration was 61 ng/L, and the highest PFOA and PFOS levels (33 and 3.6 ng/L, respectively) were also found in this sample. Maximum concentrations and occurrence frequencies (>5 ng/L) were lower in tap water samples from 15 Chinese cities analyzed for 19 PFCs than in the NJ study.21 The highest total concentration for the 19 PFCs was 130 ng/L, in Shanghai, where water was previously known to be contaminated with PFCs, followed by a total of 40 ng/L in Wuhan, and totals of 15 ng/L or less in 13 other cities. PFOA and PFHpA were found at 78 ng/L (below the NJ maximum value) and 19 ng/L (above the NJ maximum value), respectively, in Shanghai and below 5 ng/L in the other 14 cities. PFOS was found at lower frequency and concentration than in NJ (>5 ng/L in 4 of 15 cities, with a maximum of 11 ng/L). The highest levels of PFBS (18 ng/L) and PFBA (10 ng/L) in Wuhan were higher than the maxima for these PFCs in NJ; levels in the other 14 cities were well below 5 ng/L. In contrast to NJ, PFPeA, PFNA, and PFHxS were not detected above 5 ng/L in any of the Chinese cities. Finally, a Brazilian study of 24 tap water samples from 12 locations in Rio de Janeiro state, included 4 PFCs also analyzed in the NJ study (PFHxS, PFOS, PFHpA, PFOA).53 Only one detection (PFOS, 6.70 ng/L) exceeded the MRL of 5 ng/L in the NJ study. Although the number of drinking water surveys of PFCs other than PFOA and PFOS is somewhat limited, it is notable that the three highest levels of PFNA found in NJ PWS (72, 80, and 96 ng/L) exceed the maximum level reported in our review of the scientific literature (58 ng/L in tap water from Catalonia, Spain). 39 Significance of PFCs Detected in NJ PWS. A detailed evaluation of the available health effects information for the nine PFCs detected in this study is beyond the scope of this paper. As a broad generalization, the biological persistence and toxicological potency of PFCs increases with increasing carbon chain length.1 A notable exception is the human half-life of PFHxS that is longer than that of its higher chain length homologue, PFOS.1 Extensive toxicology and epidemiology data are available for PFOA and PFOS, and they are the only two PFCs with chronic toxicology studies.1 The available health effects information for the other PFCs detected in this study ranges from extremely limited to considerable. 13272

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PFBA and PFBS are much less persistent (human half-lives of 2−4 days and 10−20 days, respectively)1 than the longer chain PFCs discussed above. The highest concentration detected of each compound was very low (6 ng/L), more than 3 orders of magnitude below the Minnesota health-based groundwater values of 7000 ng/L for PFBA and 9000 ng/L for PFBS.66,67 Although its human half-life is unknown, PFHxA is excreted rapidly in both rats and monkeys, suggesting that its human half-life is also likely to be relatively short.68 The available toxicology data indicate that it is less toxic than PFOA.69,70 The highest level of PFHxA detected, 17 ng/L, is well below NJ guidance level for PFOA of 40 ng/L, which can be considered a conservative benchmark for a preliminary screening comparison. The highest levels of PFPeA and PFHpA detected in this study were 74 and 10 ng/L, respectively. No in vivo toxicology data were located for these compounds, although PFHpA is known to be rapidly excreted in rats.71 In in vitro studies comparing a series of PFCs for activation of the peroxisome proliferator receptor-α that is believed to play a role in their toxicity, these compounds were less potent than PFOA and PFNA.72 This very limited information suggests that they are less toxic than their longer chain homologues. Mixtures of PFCs are commonly present in environmental media and were detected at many of the raw water samples in this study. Although differences exist among individual PFCs, available data indicates that some PFCs cause similar effects and share common mode(s) of action.1 However, information on the effects of coexposures to multiple PFCs is extremely limited.73 Only four such studies were located,73−76 none of which were conducted in vivo in mammalian species. Additional research on the toxicological interactions among PFCs is needed so that approaches for assessing the potential risks of human exposure to these mixtures can be developed. In conclusion, PFCs were frequently found at greater than or equal to 5 ng/L in raw water from NJ PWS. At least 1 PFC was detected at 21 (70%) of 30 intakes (18 groundwater and 12 surface water) from 29 NJ PWS. Multiple PFCs (up to 8 at one site) were found in 13 of these 21 samples. Although PFOA was the most commonly detected PFC (57% of samples) and was found at the highest maximum concentration (100 ng/L), relatively high levels of other PFCs were found in some samples with little or no PFOA. Two reservoirs near an airport with some of the highest total PFC concentrations were the only sites at which total PFSAs were higher than total PFCAs. PFNA was detected more frequently (30%) and at higher concentrations (up to 96 ng/L) in NJ than in studies of raw or finished drinking water studies reported from other locations, and a possible industrial source was identified for the PWS with the PFNA highest concentration. PFDA was not detected. Future research is needed to develop approaches for assessing the potential human health risks of exposure to mixtures of PFCs found in drinking water.

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AUTHOR INFORMATION

Corresponding Author

*Phone: (609) 292-8497; e-mail: [email protected]. Notes

The views expressed are those of the authors and do not necessarily represent those of the NJ Department of Environmental Protection. The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank Barker Hamill and Vincent Monaco (NJDEP Bureau of Safe Drinking Water (BSDW), retired) for their support for this study and for their contributions to its design, Linda Walsh (NJDEP BSDW) for assistance with data management, and BSDW sampling personnel for their efforts. We are grateful to Keith Cooper (Rutgers University) and Gary Buchanan (NJDEP Office of Science) for their thorough reviews of an earlier version.

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

Tables providing the CAS numbers and structures of the PFCs analyzed, the PFC data from the PWS that were sampled, and percentage land use types within 1 km of the PWS studied. This information is available free of charge via the Internet at http:// pubs.acs.org 13273

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dx.doi.org/10.1021/es402884x | Environ. Sci. Technol. 2013, 47, 13266−13275