Environ. Sci. Technol. 2009 43, 9089–9095
Occurrence of Perfluoroalkyl Carboxylates and Sulfonates in Drinking Water Utilities and Related Waters from the United States OSCAR QUIÑONES AND S H A N E A . S N Y D E R * ,† Southern Nevada Water Authority, Applied Research and Development Center, P.O. Box 99954, Las Vegas, Nevada 89193
Received August 12, 2009. Revised manuscript received October 9, 2009. Accepted October 26, 2009.
The prevalence and persistence of perfluoroalkyl compounds (PFCs) in environmental and biological systems has been well documented, and a rising number of reports suggest that certain PFCs can result in adverse health effects in mammals. As traditional water sources become increasingly impacted by waste discharge and the demand for planned potable reuse grows, there is recent interest in determining PFC occurrence in drinking water supplies. Here we report monitoring results from drinking water treatment facility samples collected across the UnitedStates,andfromassociatedsurface,ground,andwastewater sources.Usingautomatedsolidphaseextraction(SPE)andisotopedilution liquid chromatography/tandem mass spectrometry (LC/ MS-MS), samples were screened for perfluorohexanoic acid (PFHxA), perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA) perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA), and perfluorododecanoic acid (PFDoA). Method reporting limits (MRLs) were established at 1.0 ng/L for all monitored PFCs except PFOA, for which the MRL was set at 5.0 ng/L given elevated procedural and instrumental background levels. PFOS was the only investigated PFC detected in minimally impacted surface waters, with individual site averages of 2.0 ng/L and lower. Conversely, wastewater treatment plant (WWTP) effluents and other highly impacted waters had almost 100% detection frequency for all PFCs except PFUdA and PFDoA, which were not detected above MRL in any samples. Of the investigated PFCs, PFOA averaged the highest overall concentration at any site at 115 ng/L. Substantial impacts from treated wastewater generally caused increased summedPFCconcentrationsatdownstreamdrinkingwaterfacilities, although levels and distribution suggest geographical variability. No discernible differences between influent and effluent PFC levels were observed for drinking water facilities. Removal of PFCs, however, was observed at an indirect potable reuse facility usingmicrofiltrationandreverseosmosisforwastewatertreatment, in which case all PFC levels in effluents were below the MRL.
* Corresponding author phone: (702) 856-3668; fax: (702) 8563647; e-mail:
[email protected]. † Present address (as of Spring 2010): Harvard University, Harvard School of Public Health, Department of Environmental Health Landmark Center, 4th Floor West, Room 412B 401 Park Drive Boston, MA 02215; e-mail:
[email protected]. 10.1021/es9024707 CCC: $40.75
Published on Web 11/12/2009
2009 American Chemical Society
Introduction Perfluoroalkyl compounds (PFCs) have exceptional thermal and chemical stability (1, 2) and were produced in high volumes during the second half of the 20th century to exploit their ability to repel water and oil and to reduce surface tension (2, 3). They are components of many industrial, commercial, and consumer products, and have uses as surface protectors and in firefighting foam, cosmetics, lubricants, paints, adhesives, insecticides, and food packaging (1-3). Many PFCs are impervious to environmental degradation (1) and have become practically ubiquitous in the environment via the solid and water waste processes given their resilience to wastewater treatment (4, 5). They have been detected in wastewater (4, 5), surface water (6, 7), groundwater (8, 9), and drinking water around the globe (10-12). PFCs have also been widely detected in wildlife (13-15) and in human blood serum (16-19). While associations between PFC exposure and adverse human health effects have not been consistently reported, numerous reports from animal exposure studies indicate the potential for adverse toxicological effects (20). Mean concentrations of PFOA at over 400 µg/L in blood serum from nonoccupationally exposed subjects have been reported (18), and elimination half-lives in human serum are estimated in the range of several years for PFOS, PFOA, and perfluorohexanesulfonate (PFHxS) (20). The Science Advisory Board to the U.S. Environmental Protection Agency (EPA) has recommended PFOA be classified as a likely human carcinogen (21), and both PFOS and PFOA are included in the U.S. EPA Contaminant Candidate List 3 (22). To the author’s knowledge, there are no regulatory drinking water threshold values established for any of the PFCs included in this study. However, several guideline safety values have been derived for PFOA, ranging from 40 ng/L up to 11.2 µg/L (23, 24). Attributed to changes in industrial production practices, recent U.S. population studies report reductions in mean serum concentrations for PFOA, PFOS, and PFHxS (17, 19). However, potential human health effects from exposure to these and other PFCs are likely to remain of concern given their environmental persistence and long half-life in the human body. Trace levels of pharmaceuticals and other synthetic products have been reported in drinking water supplies in the United States (25), however, reports of PFCs in the same are sparse and compound-limited. In this study, water samples were collected, extracted, and analyzed for six perfluoroalkyl carboxylates and two perfluoroalkyl sulfonates (Figure 1) during 2008. To assess PFC content in water intended for human consumption, efforts described here include monitoring of raw (influent) and finished (effluent) waters from five drinking water facilities across the United States, as well as two planned indirect potable reuse facilities. Also included are screenings of two surface water sites and a constructed wetland, each heavily impacted by treated sewage, and effluents from wastewater treatment plants (WWTPs). Water from each of these sites is believed or suspected to blend with the raw water of one of the aforementioned drinking water facilities. Furthermore, PFC monitoring results from of the Boulder Basin of Lake Mead (U.S.), the lower Colorado River (U.S.), and Lake Havasu (U.S.) are reported. The Colorado River supplies drinking water for about 30 million people and irrigates over 4 million acres of land in seven U.S. states and Mexico, including the Las Vegas metropolitan area, the Los Angeles metropolitan area via the VOL. 43, NO. 24, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 1. Perfluorinated compounds monitored in present study. Colorado River Aqueduct, and the Phoenix-Tucson metropolitan areas via the Central Arizona Project (26). The primary goal of this study was to determine occurrence of PFCs in representative U.S. drinking water supplies. In addition, we compare results to health-based drinking water protective guideline concentrations reported for PFOA (23, 24). Survey results from WWTP effluents and highly impacted sites provide additional insight as to the potential PFC contributions to drinking water supplies, and particularly in consideration of unplanned potable water reuse.
Materials and Methods Standards and Reagents. Certified standard solutions for each of the eight PFCs were purchased commercially along with corresponding isotopically labeled versions. Manufacturer assigned acronyms for isotopically labeled versions use “M” as a differentiating prefix from native PFCs; the same convention is used in this report. Sodium perfluoro-1hexanesulfonate (PFHxS), sodium perfluoro-1-hexane[18O2]sulfonate (MPFHxS), perfluoro-n-hexanoic acid (PFHxA), perfluoro-n[1,2,-13C2]-hexanoic acid (MPFHxA), sodium perfluoro-1-octanesulfonate (PFOS), sodium perfluoro-1[1,2,3,413 C4]-octanesulfonate (MPFOS), perfluoro-n-octanoic acid (PFOA), perfluoro-n[1,2,3,4-13C4]-octanoic acid (MPFOA), perfluoro-n-nonanoic acid (PFNA), perfluoro-n[1,2,3,4,513 C5)-nonanoic acid (MPFNA), perfluoro-n-decanoic acid (PFDA), perfluoro-n[1,2,-13C2]-decanoic acid (MPFDA), perfluoro-n-undecanoic acid (PFUdA), perfluoro-n[1,2,-13C2]undecanoic acid (MPFUdA), perfluoro-n-dodecanoic acid (PFDoA),andperfluoro-n[1,2-13C2]-dodecanoicacid(MPFDoA) were procured from Wellington Laboratories Inc. (Ontario, Canada). Trace analysis grade methanol was obtained from Burdick and Jackson (Muskegon, MI). Methyl-t-butyl ether (MTBE) was purchased from EM Science (Gibbstown, NJ) and ammonium acetate was obtained from J.T. Baker (Phillipsburg, NJ). Sample Sites. Sampling was coordinated to include at least one raw and one finished water sample for each quarter of 2008 from each of seven drinking water utilities across the United States, each of which produces at least 75 megaliters per day of finished product. Raw waters at these facilities included sources regarded as having no impact from treated 9090
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wastewater as well as two planned potable reuse facilities with influents composed entirely or nearly entirely of treated wastewater. The degree of wastewater impact, hereon referred to simply as impact, was estimated by utility participants according to site-specific typical hydrologic conditions. Sites and facilities with approximate wastewater contributions above 50% were designated as highly impacted, 30-50% as medium, and impacts of 5% and less as low. Table 1 describes the sampling frequency and characteristics of each participating water utility monitored in this study, as well as assigned identifiers for ease of discussion. Of seven drinking water facilities in this study, only those in Lake Havasu City, AZ (Utility 2) and Las Vegas, NV (Utility 3) had a shared source of raw water, each drawing from the Colorado River aquifer in the southwestern United States at approximately 160 km apart. In addition to drinking water utility samples, select WWTP effluents and other sites with high contents of treated wastewater were monitored during 2008. Because of their hydrologic location, these sites are considered the major potential contributors of wastewater impact to the source waters of three drinking water facilities in this study. As detailed in Table 2, effluents from WWTPs in Lake Havasu City (AZ) impact Lake Havasu and potentially raw water at Utility 2, whereas the Las Vegas Wash (NV) potentially impacts the raw water at Utility 3 as it empties into Lake Mead. Figure 2 illustrates the lower Colorado River basin, including Lake Mead and Lake Havasu, and shows sampling sites for WWTP effluent sites as well as sites in the Las Vegas Wash (LVW). The remaining highly impacted site in this study is a constructed wetland in Clayton County (GA), and considered the source of impact for raw water at Utility 5. Finally, surface water samples from sites in the Boulder Basin (BB), Hoover Dam (HD) and the lower Colorado River (LCR) were monitored during 2008, also shown in Figure 2. They were collected either monthly or quarterly, along with routine water quality samplings for these sites as established by participant utilities (Table 3). Although part of a vital drinking water supply, PFC occurrence has not been previously determined or reported for these sites. Sample Collection. Samples, duplicates, and travel blanks were collected in 1 L silanized, amber glass bottles (EaglePicher, Miami, OK). Samples were maintained at 4 °C and extracted within 14 days of sampling. Solid-Phase Extraction. Analytes were extracted in batches of six samples using 6 mL, 200 mg hydrophilic-lipophilic balance (HLB) cartridges from Waters Corporation (Millford, MA). Extractions were performed on an AutoTrace automated SPE system (Dionex Corporation, Sunnyvale, CA). The SPE cartridges were sequentially preconditioned with 5 mL of MTBE, 5 mL of methanol, and 5 mL of reagent water. Sample volumes of 1000 mL were spiked with a solution of isotopically labeled standards that contained a stable isotope of each analyte to yield a target water concentration of 10 ng/L. Samples were then loaded onto the cartridges at 15 mL/min, rinsed with 5 mL of reagent water, and subsequently dried under a nitrogen stream for 60 min. Each cartridge was then eluted with 5 mL methanol followed by 5 mL of 10/90 (v/v) methanol/MTBE, and both fractions collected in a single 15 mL calibrated centrifuge tube. The resulting extract was concentrated with a gentle stream of nitrogen to an approximate volume of 800 µL, then brought to a final volume of 1000 µL using methanol. Instrumental Analysis. An Agilent (Palo Alto, CA) G1312A binary pump and an HTC-PAL autosampler (CTC Analytics, Zwingen, Switzerland) were used for all analyses. Analytes were separated using a 75 × 4.6 mm Synergi Max-RP C12 column with a 4 µm pore size (Phenomenex, Torrance, CA). A binary gradient consisting of 0.1% formic acid (v/v) in water (A) and 100% methanol (B) at a flow rate of 700 µL/min was
TABLE 1. Description of Utility Sample Sites in Present Study Detailing Water Source and Quality, Geographical Location, Treatment Process and Frequency of Samplinga
identifier
source water
Utility 1 Utility 2 Utility 3 Utility 4 Utility 5 Utility 6*
surface water groundwater surface water surface water surface water secondary treated wastewater tertiary treated wastewater
Utility 7*
treated wastewater impact on source
location
treatment process
n influent samples screened
n effluent samples screened
3 6 30 6 5 5
3 6 33 7 7 5
5
5
NONE-control very low low med-low medium high
Aurora, CO Lake Havasu City, AZ Las Vegas, NV Minneapolis, MN Clayton County, GA Orange County, CA
COA/FLOCb, DBFc, CAMd DBFc, UVe, Clf O3g, COA/FLOCb, DBFc, CLf PACh, CAMd, DBFc CLf, COA/FLOCb, DBFc, UVe MF/ROI, UV/H2O2e,j, SATk
high
Los Angeles County, CA
CLf, DLl, SATk
a * Denotes planned indirect potable reuse facility. b Coagulation/filtration. c Deep bed filtration. d Chloramination. Medium pressure ultraviolet. f Chlorination. g Ozonation. h Powdered activated carbon. I Microfiltration/reverse osmosis. j Peroxide. k Soil Aquifer Treatment. l Dilution. e
TABLE 2. Description WWTPa Effluent Sites and Surface and Groundwater Sites Heavily Impacted by Treated Wastewater Monitored for Perfluorinated Compounds in Present Study identifier
n samples screened
sample type
site location
WWTP1 WWTP2 WWTP3
3 3 3
impacted groundwater
Lake Havasu City, AZ
Utility 2 (2%)
LVW1 LVW2
7 8
impacted groundwater
Las Vegas Wash, NV
Utility 3 (2%)
wetland
5
impacted surface water
Clayton County, GA
Utility 5 (30-50%)
a
utility impacted (estimated % impact)
Waste Water Treatment Plant.
TABLE 3. Description of Surface Water Sample Sites in the Boulder Basin (BB), Hover Dam (HD) and Lower Colorado River (LCR) Monitored for Perfluorinated Compounds in Present Study identifier
n samples screened
BB1 BB2 BB2 HD LCR1 LCR2
FIGURE 2. Regional map of the lower Colorado River indicating sampling sites for ground, surface and treated waters included in present study. used. The gradient was as follows: 5% B held for 3.5 min, increased linearly to 80% by 10 min, and held for 3 min. A 9 min equilibration step at 5% B was used at the beginning of each run to bring the total run time per sample to 22 min. An injection volume of 20 µL was used for all analyses. Contamination sources from HPLC system components can be numerous and not well characterized (27). Here, contaminants from the aqueous channel were removed using a 4.0 × 10 mm Hypercarb (Thermo Fisher Scientific, Waltham, MA) drop-in guard cartridge attached in-line before the LC purge valve. Remaining contaminants were separated from analyte peaks by installing a 30 × 4.6 mm Max-RP C12 column with a 4 µm pore size (Phenomenex, Torrance, CA) in-line upstream from the injector valve. Tandem mass spectrometry
sample type
site location
5 8 7
surface water
Boulder Basin, AZ-NV
12
surface water
Hoover Dam, AZ-NV
4 4
surface water
Lake Havasu, AZ-NV
was performed using an API 4000 triple-quadrupole mass spectrometer (Applied Biosystems, Foster City, CA). The process of optimization of the mass spectrometer has been previously published (28). Briefly, ESI negative was found to be the most sensitive and selective of the various ionization techniques/polarities. Using ESI negative ionization, the optimal compound-dependent parameters were determined and source-dependent parameters optimized. Each analyte was determined by isotope dilution with a six point calibration in the range of 1.0-50 µg/L, corresponding to 1000-fold water concentrations of 1.0-50 ng/L. Linear regression with 1/X2 was used for each analyte. Correlation coefficients were required to be at least 0.990 and typically exceeded 0.995. Method reporting limits (MRL) were based on method detection limits (MDL) calculated from seven replicate measurements of deionized water samples fortified with analytes and extracted as previously described. As an added cautionary measure, MRLs for each analyte were set conservatively at greater than five times the MDL in consideration VOL. 43, NO. 24, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 3. Box plot illustration of monitoring results for perfluorinated compounds from Boulder Basin (BB), Hoover Dam (HD), and lower Colorado River (LCR) samples. For illustrative purposes, nonpeaks are treated as zero and quantifiable values below MRL are included in the distribution box plot.
FIGURE 4. Box plot and tabulated results for perfluorinated compounds in WWTP effluents and surface (Wetland) and ground waters (LVW) highly impacted by treated wastewater. Nonpeaks are treated as zero and quantifiable values below MRL are included in the box plot distribution for illustrative purposes, but treated as zero in tabulated averages. of known and unanticipated background sources. Accounting average PFOS levels in four of five sites at 1.0-2.0 ng/L, for concentration via SPE, MRLs were set at 1.0 ng/L for all however, concentration averages of the other seven PFCs PFCs except PFOA, for which the MRL was set at 5.0 ng/L, were all below reporting limits at every site sampled. given comparatively higher procedural and instrumental Concentration levels and variability of results in these samples background levels. Data included in this report required field are illustrated in Figure 3. Aside from PFOS and PFOA, reports and SPE blanks in each sample batch to remain below for PFCs monitored in this study in surface waters of similar established MRLs for each compound. water quality are not extensive; however, reported PFOA and Data Interpretation. Data are summarized using site PFOS concentrations in samples from Lake Erie and Lake averages for individual PFC concentrations. Where summed Ontario range in the tens of ng/L in each case (7). or totals for PFC concentrations are referenced, it pertains WWTP and highly impacted sites monitored (Table 2) to the sum of said averages in each case. In all results reported had reportable concentrations of six of the eight PFCs numerically, sample concentrations below established MRLs investigated, with levels of PFUdA and PFDoA below reporting have been treated as zero in calculations. However, in aim limits at every site. The average total PFC concentrations per of a more obvious visual representation of distribution, data site ranged from 70 to 260 ng/L, with predominant contriused to construct box plots was inclusive of all quantifiable butions from PFHxA (12-79 ng/L), PFOA (26-120 ng/L), values below MRL, with nonpeaks treated as zero in every and PFOS (13-24 ng/L). Figure 4 details maximum values case. observed and average results for all PFCs monitored at these Results and Discussion sites. Surface water samples from the Boulder Basin, Hoover Dam, and the Lower Colorado River (Table 3) had reportable 9092
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Monitoring results for all drinking water facility samples (Table 1) are summarized in Figure 5.
FIGURE 5. Box plot illustrations and tabulated detection frequencies and concentrations of perfluorinated compounds observed for seven U.S. utilities with increasing impacts of treated wastewater. Nonpeaks are treated as zero and quantifiable values below MRL are included in the box plot distribution for illustrative purposes, but treated as zero in tabulated averages. Raw water at Utility 1 is regarded as nonimpacted, and in accordance, no reportable PFC levels were found in samples from this facility. Utilities 2 and 3 both had impacts on raw water estimated at approximately two percent.
However, PFCs in raw water samples from Utility 2 were distinctively higher and more diverse versus those in raw waters at Utility 3. Summed raw water concentrations at Utility 2 (23 ng/L) were mainly attributed to PFOS (10 ( 1.5 VOL. 43, NO. 24, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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ng/L) and PFOA (10 ( 1.5 ng/L), with reportable levels of PFHxA (1.0 ( 0.8 ng/L) and PFHxS (1.8 ( 1.1 ng/L) also found. In contrast, only PFOS (1.1 ( 0.9 ng/L) was detected in raw water samples at Utility 3 (Figure 5). As previously mentioned, Utilities 2 and 3 both draw raw water from the Colorado River; however, they have unique impact sources. Raw water from Lake Havasu at Utility 2 is impacted by the effluents from three WWTPs in Lake Havasu City, AZ, which in each case contained higher levels of PFCs versus those in sites from the Las Vegas Wash, which flows into Lake Mead and potentially contributes to the raw water at Utility 3 (Figure 4). Utility 4 was assessed to have 5% treated wastewater impact, but average sample concentrations for all PFCs monitored remained below reporting limits (Figure 5). No specific impact sources for Utility 4 were monitored in this study. Utility 5 results denote PFOA (31 ( 6.2 ng/L), PFHxA (29 ( 6.2 ng/L), and PFOS (22 ( 6.2 ng/L) as the major contributors to PFC total concentrations (107 ng/L). Utility 5 was estimated to have 30-50% impact from a constructed wetland composed entirely of WWTP effluent (Table 2); however, total PFC concentrations in raw water samples at this utility were approximately 60% of those found in the constructed wetland (Figure 4). Utilities 6 and 7 contained comparable amounts of total monitored PFCs in influent samples (80 ng/L), and in each case PFOS and PFOA accounted for slightly over 70% of the total PFCs (Figure 5). Utility 6 and 7 are planned indirect potable reuse facilities with a shared geographical location (Southern California) with impacts of 98 and 100%, respectively. Comparable PFC concentrations have been reported for WWTP effluent samples in the United States (4, 5), generally ranging in concentration from one to several hundred ng/L. As a whole, PFC levels were considerably higher in raw waters with higher degrees of wastewater impact. However, as noted with utilities 2 and 3, samples with shared water supplies and equivalent levels of impact can have markedly different distributions and levels of PFCs. Likewise, results observed in utilities 5 through 7 indicate that even substantial increases in degree of impact do not necessarily result in higher PFC concentrations, emphasizing the importance of wastewater composition and the unique conditions at the influent water source. Similar variability has been reported in waters from diverse sources around the world (9). Compound-specific concentrations in finished drinking water samples were comparable to levels in raw water samples in almost every case (Figure 5), adding to the data that demonstrate PFC resilience during drinking water treatment (4, 5). The only removal observed in this study was at utility 6, the sole facility in this study employing microfiltration and reverse osmosis in wastewater treatment for indirect potable reuse. Effluents contained no reportable levels for any monitored compound, in contrast to total PFC influent levels of 80 ng/L and PFOS averages of 41 ( 18 ng/L. Effective removal of PFOS by reverse osmosis treatment has been previously documented (29). As previously observed (9), overall frequency and levels of detection in this study were greater for PFCs eight or less carbons in length, in this case PFOS, PFOA, PFHxS, and PFHxA. Regulatory drinking water protective values are not, to the author’s knowledge, established for any compound investigated in this study. Several guideline values have been reported for PFOA, however, they are substantially variable. Most conservatively, the New Jersey Department of Environmental Protection reported a health-based drinking water concentration protective for lifetime exposure for PFOA at 40 ng/L (24), developed from toxicological end points identified in a draft EPA risk assessment (21). However, other 9094
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reported guideline values derived for PFOA range as high as 11.2 µg/L (25). To the best of the author’s knowledge, guideline reference values have not been reported for other PFCs surveyed in this study. Concentrations of PFOA in Lake Mead, the lower Colorado River, and all drinking water utilities monitored in this study were below 40 ng/L, the most conservative health-based guidance levels reported. While PFOA and PFOS were predominant in this study, PFHxA and PFHxS also had significant, and at times, comparable contributions to total PFC load. Given the values observed for PFOS, PFOA, and other PFCs in WWTP effluents and highly impacted waters, it is probable that increasing WWTP effluents and increasing demands for water reuse will lead to greater PFC loading to drinking water sources. Therefore, a better understanding of the distribution, toxicity, and fate of PFCs remains essential as it pertains to human health and to PFC burden on the environment in general.
Acknowledgments We thank Jörg Drewes and Eric Dickenson from the Colorado School of Mines, and Mark Benotti and Fernando Rosario from the Southern Nevada Water Authority for their invaluable contributions to this work. We also thank Water Quality Research and Development team at the Southern Nevada Water Authority for their continued support. This work was partially supported by the Water Reuse Foundation (project 06-006).
Supporting Information Available Additional information on analytical methods and method quality assurance is provided for reference. This material is available free of charge via the Internet at http://pubs.acs.org/.
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