Amy D. Delinsky

Application of WWTP Biosolids and Resulting Perfluorinated Compound Contamination of Surface and Well Water in Decatur, Alabama, USA

Perfluorinated chemicals (PFCs) such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been produced and used in a wide range of industrial and consumer products for many decades. Their resistance to degradation has led to their widespread distribution in the environment, but little is known about how humans become exposed. Recent studies have demonstrated that the application of PFC contaminated biosolids can have important effects on local environments, ultimately leading to demonstrable human exposures. This manuscript describes a situation in Decatur, Alabama where PFC contaminated biosolids from a local municipal wastewater treatment facility that had received waste from local fluorochemical facilities were used as a soil amendment in local agricultural fields for as many as twelve years. Ten target PFCs were measured in surface and groundwater samples. Results show that surface and well water in the vicinity of these fields had elevated PFC concentrations, with 22% of the samples exceeding the U.S. Environmental Protection Agencys Provisional Health Advisory level for PFOA in drinking water of 400 ng/L. Water/soil concentration ratios as high as 0.34 for perfluorohexanoic acid, 0.17 for perfluoroheptanoic acid, and 0.04 for PFOA verify decreasing mobility from soils with increasing chain length while indicating that relatively high transport from soils to surface and well water is possible.

Determination of perfluorinated compounds in the upper Mississippi river basin.

Despite ongoing efforts to develop robust analytical methods for the determination of perfluorinated compounds (PFCs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in surface water, comparatively little has been published on method performance, and the environmental distribution of these materials remains poorly described worldwide. In this study, an existing method was improved and applied in a large-scale evaluation of the Upper Mississippi River Basin, one of the largest watersheds in the world. Samples were collected in 2008 in an effort that involved multiple sample sites and collection teams, long-range transport, and storage of up to 4 weeks before analysis. Ninety-four percent of the resulting 177 samples had quantifiable PFC concentrations, with 80% of the individual target compounds below 10 ng/L. The most abundant PFCs were perfluorobutanoic acid (C4; 77% above the limit of quantitation, LOQ), perfluorooctanoic acid (C8; 73%), perfluorooctanesulfonate (PFOS; 71%), perfluorohexanoic acid (C6; 70%), and perfluoroheptanoic acid (C7; 69%), with the remaining target compounds occurring above the LOQ in less than 50% of the samples. The highest concentrations recorded include C4 at 458 ng/L, PFOS at 245 ng/L, and C8 at 125 ng/L, suggesting various point source inputs within the Basin.

Perfluorinated compounds in common carp (Cyprinus carpio) fillets from the Upper Mississippi River

Ten different perfluoroalkyl acids (PFAAs), including perfluooctane sulfonate (PFOS), were measured in 30 common carp (Cyprinus carpio) fillets collected from three sites on the Upper Mississippi River in Minnesota in an effort to evaluate the potential impact of PFAA emissions in this area. Samples upstream of the city of St. Cloud (reference site) had median PFOS concentrations of 8.1 ng/g wet weight (ng/g wet wt), but median levels increased significantly downstream in the Minneapolis-St. Paul urban area, with concentrations from the Pigs Eye Lake site at 26 ng/g wet wt (p = 0.0015) and the Spring Lake site at 40 ng/g wet wt (p = 0.0004). This latter PFOS concentration is within the advisory range for limiting fish consumption to one meal a week according to the Minnesota Department of Health. Other PFAAs were also found to increase significantly between the reference site and the Minneapolis-St. Paul area, but maximal concentrations remained below 2.0 ng/g wet wt. This study demonstrates the bioaccumulation of PFAAs in a ubiquitous fish species in a major urban area known to have historical inputs of various PFAA compounds. The full extent of this contamination and the potential for accumulation in other species remain to be evaluated.

Comparative pharmacokinetics of perfluorononanoic acid in rat and mouse

Perfluorononanoic acid (PFNA) is a fluorinated organic chemical found at low levels in the environment, but is detectable in humans and wildlife. The present study compared the pharmacokinetic properties of PFNA in two laboratory rodent species. Male and female Sprague-Dawley rats were given a single dose of PFNA by oral gavage at 1, 3, or 10mg/kg, and blood was collected from the tail vein at 1, 2, 3, 4, 7, 16, 21, 28, 35, 42 and 50 days after treatment. In addition, livers and kidneys were collected for PFNA analysis at the terminal time point. CD-1 mice were given a single oral dose of PFNA of 1 or 10mg/kg, and 4 males and 4 females were killed at similar time intervals; trunk blood, liver and kidney were collected. Serum and tissue concentrations of PFNA were determined by LC-MS/MS. Serum elimination of PFNA is by and large linear with exposure doses in the rat; however, like PFOA, a major sex difference in the rate of elimination is observed, with an estimated half-life of 30.6 days for males and 1.4 days for females. PFNA is stored preferentially in the liver but not in the kidneys. In the mouse, the rates of PFNA serum elimination are non-linear with exposure dose and are slightly faster in females than males, with terminal estimated serum half-life of 25.8-68.4 days and 34.3-68.9 days, respectively. PFNA is also stored preferentially in the mouse liver but not in the kidneys. Hepatic uptake appears to be more efficient and storage capacity greater in male mice than in females. These data suggest that (1) PFNA is more persistent in the mouse than in the rat; (2) there is a major sex difference in the serum elimination of PFNA in the rat, but much less so in the mouse; and (3) there is a significantly higher hepatic accumulation of PFNA in male mice than in females.

Determination of ten perfluorinated compounds in bluegill sunfish (Lepomis macrochirus) fillets

A rigorous solid phase extraction/liquid chromatography/tandem mass spectrometry method for the measurement of 10 perfluorinated compounds (PFCs) in fish fillets is described and applied to fillets of bluegill sunfish (Lepomis macrochirus) collected from selected areas of Minnesota and North Carolina. The 4 PFC analytes routinely detected in bluegill fillets were perfluorooctane sulfonate (PFOS), perfluorodecanoic acid (C10), perfluoroundecanoic acid (C11), and perflurododecanoic acid (C12). Measures of method accuracy and precision for these compounds showed that calculated concentrations of PFCs in spiked samples differed by less than 20% from their theoretical values and that the %RSD for repeated measurements was less than 20%. Minnesota samples were collected from areas of the Mississippi River near historical PFC sources, from the St. Croix River as a background site, and from Lake Calhoun, which has no documented PFC sources. PFOS was the most prevalent PFC found in the Minnesota samples, with median concentrations of 47.0-102 ng/g at locations along the Mississippi River, 2.08 ng/g in the St. Croix River, and 275 ng/g in Lake Calhoun. North Carolina samples were collected from two rivers with no known historical PFC sources. PFOS was the predominant analyte in fish taken from the Haw and Deep Rivers, with median concentrations of 30.3 and 62.2 ng/g, respectively. Concentrations of C10, C11, and C12 in NC samples were among the highest reported in the literature, with respective median values of 9.08, 23.9, and 6.60 ng/g in fish from the Haw River and 2.90, 9.15, and 3.46 ng/g in fish from the Deep River. These results suggest that PFC contamination in freshwater fish may not be limited to areas with known historical PFC inputs.

Determination of perfluorinated alkyl acid concentrations in biological standard reference materials

AbstractStandard reference materials (SRMs) are homogeneous, well-characterized materials used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of SRMs that have mass fraction values assigned for legacy pollutants. These SRMs can also serve as test materials for method development, method validation, and measurement for contaminants of emerging concern. Because inter-laboratory comparison studies have revealed substantial variability of measurements of perfluoroalkyl acids (PFAAs), future analytical measurements will benefit from determination of consensus values for PFAAs in SRMs to provide a means to demonstrate method-specific performance. To that end, NIST, in collaboration with other groups, has been measuring concentrations of PFAAs in a variety of SRMs. Here we report levels of PFAAs and perfluorooctane sulfonamide (PFOSA) determined in four biological SRMs: fish tissue (SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue), bovine liver (SRM 1577c), and mussel tissue (SRM 2974a). We also report concentrations for three in-house quality-control materials: beluga whale liver, pygmy sperm whale liver, and white-sided dolphin liver. Measurements in SRMs show an array of PFAAs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Reference and information values are reported for PFAAs measured in these biological SRMs. FigureNIST SRMs 1946 Lake Superior Fish Tissue and 1947 Lake Michigan Fish Tissue

Analysis of PFOA in dosed CD1 mice: Part 1. Methods development for the analysis of tissues and fluids from pregnant and lactating mice and their pups

The number of studies involving the analysis of perfluorooctanoic acid (PFOA) has increased recently because PFOA is routinely detected in human blood samples from around the world. Recent studies with mice have shown that dosing pregnant dams with PFOA during gestation gives rise to a dose-dependent mortality in the litters, a reduction in neonatal body weight for the surviving pups, and subsequent deficits in mammary gland development when compared to control animals. The actual body burdens of PFOA in dams and pups associated with these endpoints have not been determined, in part due to a lack of robust analytical methods for these matrices. The goal of the current study was to develop reliable methods with acceptable performance characteristics for the analysis of PFOA in several matrices relevant to pregnant mouse studies. Dam and pup serum, amniotic fluid, urine, milk, mammary tissue, and whole mouse pups were isolated for method development and analysis. The resulting method provided excellent accuracy (92.1-111%) and reproducibility (relative standard deviation 4.3-21%) making them very useful for future studies. These methods were then applied to dosed animal fluids and tissues in order to conduct a thorough evaluation of the pharmacokinetics in utero. Resulting tissue specific measurements of PFOA in serum, amniotic fluid, urine, milk, mammary tissue, and whole pup homogenate will be used to more completely describe the dose-response relationships for the most sensitive health outcomes and inform pharmacokinetic models that are being developed and evaluated.

Method Development and Measurement of Perfluorinated Compounds in U.S. Chicken Eggs.

We have found a systematic error in our paper (DOI: 10.1021/es800770f; published on the Web 07/23/2008) that has led us to report PFOS in U.S. chicken eggs at levels that are incorrect. After careful examination of our data, we conclude that there is little evidence of perfluorooctane sulfonate (PFOS) in these eggs at any concentration above 0.5 ng/g wet weight. The error for PFOS comes from using the transition 499 m/zf 80 m/z to quantify, but not also using the 499 m/zf 99 m/z to confirm the presence of PFOS in these samples. Upon further analysis of our data, we identified a coeluting peak that undergoes the 499 m/z f 80 m/z transition but which does not also produce a consistent 499 m/z f 99 m/z transition that would confirm the presence of PFOS. While we listed the parentf daughter transitions and the confirmatory ions in the Supporting Information of the manuscript, we did not systematically confirm that the quantitation ion/confirmatory ion ratio was in the same range for both the standards and the unknown samples. During the preliminary phase of this work we checked to see if taurodeoxycholate, another recently identified material that also gives a 499m/zf 80m/z transition, was present in these samples, and we found that it eluted well after PFOS using the conditions listed in the Methods section. Recent reanalysis of these egg samples using an ion trap time-of-flight mass spectrometer provided evidence that the coeluting PFOS interferent was likely to be a different isomer of taurodeoxycholate. It is likely that a better approach would be to use longer chromatographic run times to achieve separation of target compounds from potential interferents, use of 499 m/z f 99 m/z for quantitation, and monitoring confirmatory daughter ion(s) to ensure that ion ratios for standards and unknowns are consistent. We have reanalyzed the data for the other compounds listed in the paper, and while there are few samples with measurable concentrations, we believe these data are accurate. Studies which document the bioaccumulation of the PFCs in certain food webs and the tissue-specific concentration of PFCs in certain organs (e.g., liver) suggest that food may be an important source of exposure for humans. We believe that a commodity-specific approach for the evaluation of individual food items will be a useful method for determining the presence of perfluorinated compounds in diet. Considering the errors listed above, we have withdrawn this paper from publication.