PFAS ghosts: how to identify, evaluate, and exorcise new and existing analytical interference.

With increasing public awareness of PFAS, and their presence in biological and environmental media across the globe, comes a matching increase in the number of PFAS monitoring studies. As more matrices and sample cohorts are examined, there are more opportunities for matrix interferents to appear as PFAS where there are none (i.e., "seeing ghosts"), impacting subsequent reports. Addressing these ghosts is vital for the research community, as proper analytical measurements are necessary for decision-makers to understand the presence, levels, and potential risks associated with PFAS and protect human and environmental health. To date, PFAS interference has been identified in several matrices (e.g., food, shellfish, blood, tissue); however, additional unidentified interferents are likely to be observed as PFAS research continues to expand. Therefore, the aim of this commentary is several fold: (1) to create and support a publicly available dataset of all currently known PFAS analytical interferents, (2) to allow for the expansion of that dataset as more sources of interference are identified, and (3) to advise the wider scientific community on how to both identify and eliminate current or new analytical interference in PFAS analyses.

Analyte and matrix method extension of per- and polyfluoroalkyl substances in food and feed.

The development and expansion of analytical methods for per- and polyfluoroalkyl substances (PFAS) in food are essential for the continued monitoring of the United States (US) food supply and assessments of dietary exposure. In March 2022, the European Union Reference Laboratory for Halogenated Persistent Organic Pollutants in Feed and Food (EURL POPs) released a guidance document covering priority PFAS of interest, including analytical method parameters and limits of quantification (LOQs). As a result, the Food and Drug Administration (FDA) began method extension work to incorporate ten new additional analytes to method C-010.02 including long-chain perfluorosulfonic acids, fluorotelomer sulfonates, and perfluorooctane sulfonamide. Four long-chain carboxylic acids were also validated across all foods, which were previously added to C-010.02 but only validated in seafood. In December 2022, the European Union published Commission Regulation 2022/2388, establishing maximum levels for perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorohexane sulfonic acid (PFHxS) in certain foodstuffs, primarily fish, molluscs, crustaceans, and eggs. As a result, the FDA method was evaluated for performance in reaching LOQs defined in Commission Regulation (EU) 2022/1431. The FDA method was found to be able to reach all required LOQs for analytes in matrices with established maximum levels. Currently, method detection limits (MDLs), which are used by the FDA as the lower limit for reporting PFAS in surveillance samples, were in the same range as defined indicative levels. With further method modifications, required LOQs could be met in fruits, vegetables, and milk. Reaching the lower targeted LOQs for these food matrices will require moving the method to an instrument that can provide increased signal:noise gains at the lower limits of quantification.

Plasma and Skin Per- and Polyfluoroalkyl Substance (PFAS) Levels in Dairy Cattle with Lifetime Exposures to PFAS-Contaminated Drinking Water and Feed.

Plasma and ear notch samples were removed from 164 Holstein cows and heifers, which had lifetime exposures to per- and polyfluoroalkyl substances (PFAS) through consumption of contaminated feed and water sources. A suite of nine PFAS including five perfluoroalkyl carboxylic acids (PFCA) and four perfluoroalkyl sulfonic acids (PFSA) was quantified in plasma and ear notch samples by liquid chromatography-mass spectrometry. Bioaccumulation of four- to nine-carbon PFCAs did not occur in plasma or skin, but PFSAs longer than four carbons accumulated in both plasma and skin. Exposure periods of at least 1 year were necessary for PFSAs to reach steady-state concentrations in plasma. Neither parity (P = 0.76) nor lactation status (P = 0.30) affected total PFSA concentrations in mature cow plasma. In contrast, lactation status greatly affected (P < 0.0001) total PFSA concentrations in ear notch samples. Skin samples could be used for biomonitoring purposes in instances when on-farm blood collection and plasma preparation are not practical.

Analysis of Per- and Poly(fluoroalkyl) Substances (PFASs) in Highly Consumed Seafood Products from U.S. Markets.

Seafood consumption has been identified as one of the major contributors of per- and poly(fluoroalkyl) substances (PFASs) to the human diet. To assess dietary exposure, highly consumed seafood products in the United States were selected for analysis. The analytical method previously used for processed food was extended to include four additional long-chain perflurocarboxylic acids (PFCAs), which have been reported in seafood samples. This method was single-lab-validated, and method detection limits were reported at 345 ng kg-1 for perfluorobutanoic acid (PFBA) and 207 ng kg-1 for perfluoropentanoic acid (PFPeA) and below 100 ng kg-1 for the rest of the PFAS analytes. The 81 seafood samples (clams, crab, tuna, shrimp, tilapia, cod, salmon, pollock) were analyzed for 20 PFASs using the updated analytical method. Most of the seafood packaging was also analyzed by Fourier transform infrared-attenuated total reflectance (FTIR-ATR) to identify packaging potentially coated with PFASs. None of the packaging samples in this study were identified as having PFASs. A wide range of concentrations was observed among the seafood samples, ranging from below the method detection limit to the highest concentration of 23 µg kg-1 for the sum of PFASs in one of the canned clam samples. Such a wide range is consistent with those reported in previous studies. The highest concentrations were reported in clams and crabs, followed by cod, tuna, pollock, tilapia, salmon, and shrimp. Technical perfluorooctanoic acid (PFOA) dominated the profile of the clam samples, which has been consistently found in other clam samples, especially in Asia. Long-chain PFCAs, specifically perfluoroundecanoic (PFUdA) and perfluorododecanoic (PFDoA), were the most frequently detected analytes across all seafood samples. The trends observed are comparable with those in the literature where benthic organisms tend to have the highest PFAS concentrations, followed by lean fish, fatty fish, and aquaculture. The results from this study will be used to prioritize future studies and to inform steps to reduce consumer exposure to PFASs.

Large volume headspace GC/MS analysis for the identification of volatile compounds relating to seafood decomposition.

Decomposition in seafood products in the United States is monitored by the Food and Drug Administration (FDA) laboratories using sensory testing, which requires highly trained analysts. A large-volume headspace (LVHS) gas chromatography/mass spectrometry (GC/MS) method was developed to generate analytical results that can be directly compared to sensory evaluation. Headspace vapor was withdrawn from a 1-L vial containing 50 g seafood sample using a large volume headspace autosampler. Various volatile compounds were collected simultaneously. Analytes were preconcentrated by a capillary column trapping system and then sent through a cryo-focuser mounted onto the GC injector. A selected ion monitoring (SIM) MS acquisition method was used to selectively monitor 38 compounds of interest. Samples of red snapper, croaker, weakfish, mahi-mahi, black tiger shrimp, yellowfin tuna, and sockeye salmon that have been assessed and scored by an FDA National Seafood Sensory Expert (NSSE) were used for method performance evaluation. Characteristic compounds potentially associated with seafood quality deterioration for each seafood species were identified by quantitative analysis using pooled matrix-matched calibrations and two-sample t-test statistical analysis. Classification of fresh and decomposed samples was visualized on the analysis of variance (ANOVA)-principal component analysis (PCA) score plots. The results determined that the LVHS-GC/MS technique appeared promising as a screening tool to identify compounds representative of sensory analysis.

Analysis of per- and poly-fluoroalkyl substances (PFAS) in processed foods from FDA's Total Diet Study.

Additional occurrence data are needed to better understand human exposure to per- and poly-fluoroalkyl substances (PFAS) from commercially available foods in the United States. The Food and Drug Administration's (FDA) Total Diet Study (TDS) collects foods that are both nationally and regionally distributed. In 2018, 172 processed foods were collected from grocery stores around Lenexa, KS, as part of the TDS national collection. A previously developed method for the analysis of PFAS in foods as part of the TDS regional collection was modified and optimized for these samples. This method was single lab validated using 5 different matrices and method detection limits were calculated. During the analysis of these samples, challenges arose with method blanks and further investigation into statistical methods to distinguish between blank and sample concentrations were done. The confirmation of two short chain PFAS, perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPeA), was not possible using triple quadrupole mass spectrometry and a confirmation method was developed using high-resolution mass spectrometry. This technique was also used to investigate potential detections and interferents that fell within the retention time criteria for positive detections. In the national collection, positive detections of perfluorooctanesulfonic acid (PFOS) and perfluorononanoic acid (PFNA) were found in frozen fish sticks/patties, PFOS and perfluorodecanoic acid (PFDA) in canned tuna, and PFOS in protein powder. Concentrations were all below 150 ppt, and no other detects were confirmed above the method detection limits in any other foods.

Method Development and Validation of Per- and Polyfluoroalkyl Substances in Foods from FDA's Total Diet Study Program.

Human exposure to per- and polyfluoroalkyl substances (PFAS) through the US diet has not been well-characterized. Highly consumed foods are routinely monitored through FDA's Total Diet Study program. Portions of these samples were used to develop and validate a method for PFAS in a wide variety of foods. The extraction of 16 PFAS was performed using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and analyzed by liquid chromatography/mass spectrometry. Method optimizations are described including investigations into the QuEChERS sorbents, matrix effects, and solid-phase extraction (SPE) cartridges. The use of a custom push-through SPE cartridge showed promising results as a rapid cleanup option for food samples. Challenges in ion confirmation are discussed, and the use of enhanced product ion (EPI) full-scan MS/MS spectra is presented as a potential option for verifying false positives. The validated method was then used for the analysis of 179 total diet study samples, and positive detects for perfluorooctanesulfonic acid (PFOS) were found in two fish and one meat sample.

Investigation into the Concentrations and Sources of Nitrates and Nitrites in Milk and Plant-Based Powders.

Milk powders in the United States (US) may contain nitrates and nitrites from several potential sources. These sources include the ingestion of nitrates and nitrites by dairy cows during grazing and drinking, nitric acid used during the sanitization of dairy equipment, and the production of nitrous oxides in directly heated spray dryers. Recently, milk powders manufactured in the US have been rejected during import to other countries because nitrite concentrations were greater than 2 mg/kg (ppm). To date, the concentrations of nitrates and nitrites in milk and plant-based powders in the US are unknown. In this study the nitrate and nitrite concentrations present in diverse milk powders were investigated including 81 milk powders from local and online retailers from 2015 to 2018. In addition, 71 commercial milk powders were obtained from blinded production facilities. Nitrate and nitrite concentrations were determined using ion chromatography with conductivity and UV detection. A subset of samples was analyzed for N-nitrosodimethylamine using gas chromatography-mass spectrometry. Carbon and nitrogen bulk isotope ratios analyzed using isotope ratio mass spectrometry were used to obtain some insights into the production method (organic vs conventional) and geographic source of the milk powder samples. Background nitrate concentrations in US-produced milk powder samples averaged 17 ± 12 mg/kg. Nitrite was detected at concentrations greater than 2 mg/kg in 5 out of 39 different brands of retail milk and plant-based powders. Of these brands, two were plant-based (soy and coconut) powders and the other three had consistently high nitrites. The analysis of milk powders using stable isotope analysis revealed further information about the cow's diet.

Determination of endogenous concentrations of nitrites and nitrates in different types of cheese in the United States: method development and validation using ion chromatography.

Nitrites and nitrates can be present in dairy products from both endogenous and exogenous sources. In the European Union (EU), 150 mg kg-1 of nitrates are allowed to be added to the cheese milk during the manufacturing process. The CODEX General Standard for Food Additives has a maximum permitted level of 50 mg kg-1 residue in cheese, while in the United States (U.S.) nitrates are unapproved for use as food additives in cheese. In order to be able to investigate imported cheeses for nitrates intentionally added as preservatives and the endogenous concentrations of nitrates and nitrites present in cheeses in the U.S. marketplace, a method was developed and validated using ion chromatography with conductivity detection. A market sampling of cheese samples purchased in the Washington DC metro area was performed. In 64 samples of cheese, concentrations ranged from below the method detection limit (MDL) to 26 mg kg-1 for nitrates and no concentrations of nitrites were found in any of the cheese samples above the MDL of 0.1 mg kg-1. A majority of the samples (93%) had concentrations below 10 mg kg-1, which indicate the presence of endogenous nitrates. The samples with concentrations above 10 mg kg-1 were mainly processed cheese spread, which can contain additional ingredients often of plant-based origin. These ingredients are likely the cause of the elevated nitrate concentrations. The analysis of 12 additional cheese samples that are liable to the intentional addition of nitrates, 9 of which were imported, indicated that in this limited study, concentrations of nitrate in the U.S.-produced cheeses did not differ from those in imported samples.

Investigation into perfluoroalkyl substances (PFASs) in a cranberry bog: method development and sampling results.

The contamination of groundwater and surface water from previous uses of perfluoroalkyl substances (PFASs), particularly products containing the contaminants perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), has become a concern for drinking water and as a potential exposure route to the food supply. In 2016, the Food and Drug Administration (FDA) was asked to investigate a bog in Massachusetts where the surface water was believed to be contaminated with PFASs. As a result, a method was developed for the analysis of PFASs in cranberries, and water and fruit from the affected bog were evaluated. A QuEChERS method was developed and validated for PFOA, PFOS, and six additional shorter-chain PFASs. Method recoveries ranged from 60% to 115% for validation spikes performed at 10, 20 and 40 ng g-1 and method detection limits ranged from 0.2 to 5.6 ng g-1. Bog water samples were analysed using Environmental Protection Agency (EPA) method 537 for PFOA, PFOS and four additional short-chain PFASs. Surface water concentrations for PFOS ranged from 16 to 122 ng L-1 and input water concentrations were 132 ng L-1 and 206 ng L-1. Of the eight water samples, seven had water concentrations that exceeded the EPA health advisory level for PFOS of 70 ng L-1. Of the 42 cranberry samples analysed, none had detects of PFOA or PFOS above their method detection limits (0.4 and 0.5 ng g-1, respectively), nor any of the other short-chain PFASs.

Simultaneous Analysis of 3-MCPD and 1,3-DCP in Asian Style Sauces Using QuEChERS Extraction and Gas Chromatography-Triple Quadrupole Mass Spectrometry.

Acid hydrolyzed vegetable protein (aHVP) is used for flavoring a wide variety of foods and also in the production of nonfermented soy sauce. During the production of aHVP, chloropropanols including 3-monochloropropane-1,2-diol (3-MCPD) and 1,3 dichloropropane-2-ol (1,3-DCP) can be formed through the reaction of the hydrochloric acid catalyst and residual fat and the reaction of 3-MCPD with acetic acid, respectively. 3-MCPD is a carcinogen, and 1,3-DCP has been classified as a genotoxic carcinogen. The European Union (EU) has set a maximum concentration of 0.02 mg/kg of 3-MCPD in aHVP, and the Food and Drug Administration (FDA) set a guidance limit of 1 mg/kg of 3-MCPD in aHVP. 1,3-DCP is not an approved food additive, and the Joint FAO/WHO Expert Committee on Food Additives (JEFCA) has set a limit at 0.005 mg/kg, which is close to the estimated method detection limit. Currently there are few analytical methods for the simultaneous determination of 3-MCPD and 1,3-DCP without derivatization due to differences in their physical chemical properties and reactivity. A new method was developed using QuEChERS (quick, easy, cheap, effective, rugged, and safe) with direct analysis of the extract without derivatization using gas chromatography-triple quadrupole mass spectrometry (GC-QQQ). Additionally, a market sampling of 60 soy sauce samples was performed in 2015 to determine if concentrations have changed since the FDA limit was set in 2008. The sampling results were compared between the new QuEChERS method and a method using phenylboronic acid (PBA) as a derivatizing agent for 3-MCPD analysis. The concentrations of 3-MCPD detected in soy sauce samples collected in 2015 (

Suitability of polystyrene as a functional barrier layer in coloured food contact materials.

Functional barriers in food contact materials (FCMs) are used to prevent or reduce migration from inner layers in multilayer structures to food. The effectiveness of functional barrier layers was investigated in coloured polystyrene (PS) bowls due to their intended condition of use with hot liquids such as soups or stew. Migration experiments were performed over a 10-day period using USFDA-recommended food simulants (10% ethanol, 50% ethanol, corn oil and Miglyol) along with several other food oils. At the end of the 10 days, solvent dyes had migrated from the PS bowls at 12, 1 and 31,000 ng cm(-)(2) into coconut oil, palm kernel oil and Miglyol respectively, and in coconut oil and Miglyol the colour change was visible to the human eye. Scanning electron microscope (SEM) images revealed that the functional barrier was no longer intact for the bowls exposed to coconut oil, palm kernel oil, Miglyol, 10% ethanol, 50% ethanol and goat's milk. Additional tests showed that 1-dodecanol, a lauryl alcohol derived from palm kernel oil and coconut oil, was present in the PS bowls at an average concentration of 11 mg kg(-1). This compound is likely to have been used as a dispersing agent for the solvent dye and aided the migration of the solvent dye from the PS bowl into the food simulant. The solvent dye was not found in the 10% ethanol, 50% ethanol and goat's milk food simulants above their respective limits of detection, which is likely to be due to its insolubility in aqueous solutions. A disrupted barrier layer is of concern because if there are unregulated materials in the inner layers of the laminate, they may migrate to food, and therefore be considered unapproved food additives resulting in the food being deemed adulterated under the Federal Food Drug and Cosmetic Act.

Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants.

Due to the 2011 labelling of styrene monomer as "reasonably anticipated to be a human carcinogen" by the National Institutes of Health's National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg(-1) for the styrene monomer, 130-2900 mg kg(-1) for the sum of three styrene dimers, and 220-16,000 mg kg(-1) for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g(-1); dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g(-1) and trimer concentrations were all below the LOQ (2 ng g(-1)). Diffusion coefficients (Dp) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10(2) to 2 × 10(6)) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.

Assessments and improvements in methods for monitoring seafood safety in response to the Deepwater Horizon oil spill.

As a result of the April 2010 Deepwater Horizon oil spill, sensory testing protocols were established for reopening closed seafood harvest areas. In order to improve this method and quantitatively assess petrochemical taint, a new method using solid phase microextraction (SPME) and a 5975T transportable GC/MS was developed. This method can analyze 40 samples per instrument per day and could be an alternative to the human sensory panel. In seafood samples collected from supermarkets in the Washington D.C. area and the Gulf of Mexico, all compounds related to petrochemical taint were below the method detection limit (MDL) (0.14-2.6 ng/g). Additionally, to address consumer concerns regarding the presence of n-alkanes and iso-alkanes in seafood, these compounds were investigated in samples purchased in the Washington D.C. area and the Gulf of Mexico. Concentrations in Gulf of Mexico finfish ranged from 0.066 to 1.2 mg/kg, which is within the same background range of iso- and n-alkanes measured in seafood samples purchased in the Washington D.C. area (0.0072-1.6 µg/g). These automated methods provide a transportable option to obtain rapid results for compounds indicative of petroleum taint and iso- and n-alkanes in case of a future disaster.

Rapidly equilibrating micrometer film sampler for priority pollutants in air.

Modified polymer-coated glass samplers (POGs), termed EVA samplers, consist of micrometer-thin layers of ethylene vinyl acetate (EVA) coated onto a glass fiber filter or aluminum foil substrate. These samplers were designed to equilibrate rapidly with priority pollutants in air, making them ideal for short-term spatial studies in ambient or indoor air. The EVA sampler was calibrated by measuring the uptake of polychlorinated biphenyls (PCBs) over 8 weeks in an indoor environment, and four different film thicknesses were monitored that ranged from 0.1 to 30 µm. The results were used to calculate the average mass transfer coefficient (50.5 m/day) and generate contour maps that provide guidance in choosing an appropriate EVA sampler for a particular study based on film thickness, deployment time, and the log K(OA) of the anlayte. A range of air pollutant classes was also added to the EVA sampler prior to deployment to assess depuration rates. These included polychlorinated biphenyls (PCBs), current-use pesticides (CUPs), perfluorinated compounds (PFCs), and polybrominated diphenyl ethers (PBDEs). On the basis of the depuration profiles, the EVA sampler was a suitable equilibrium sampler for several CUPs and PCBs; however, for the high molecular weight PCBs and PBDEs, the EVA sampler operates as a linear uptake sampler. Samplers were also evaluated for their use as a rapid screening tool for assessing concentrations of siloxanes in indoor air. The EVA sampler was used to estimate air concentrations for D4 and D5 in laboratory air to be 118 and 89 ng/m(3), respectively. Analyses were performed directly using thermal desorption gas chromatography/mass spectrometry (TDS-GC-MS). EVA samplers show promise due to their relatively low cost and ease of deployment and applicability to a wide range of priority chemicals. The ability to alter the film thickness, and hence the sorption capacity and performance of the EVA sampler, allows for a versatile sampler that can be used under varying sampling conditions and deployment times.

Application of sorbent impregnated polyurethane foam (SIP) disk passive air samplers for investigating organochlorine pesticides and polybrominated diphenyl ethers at the global scale.

As part of continued efforts under the Global Atmospheric Passive Sampling (GAPS) Network to develop passive air samplers applicable to a wide-range of compounds, sorbent-impregnated polyurethane foam (SIP) disk samplers were codeployed and tested against conventional polyurethane foam (PUF) disk samplers. The SIP disk sampler has a higher sorptive capacity compared to the PUF disk sampler, due to its impregnation with ground XAD resin. The two sampler types were codeployed at 20 sites during the 2009, 3-month long spring sampling period of the GAPS Network. Air concentrations for chlordanes (trans-chlordane, cis-chlordane, and trans-nonachlor) and endosulfans (endosulfan I, endosulfan II, and endosulfan sulfate) derived from PUF disk and SIP disk samplers showed near 1:1 agreement and confirmed previous results for polychlorinated biphenyls (PCBs). Discrepancies observed for α-HCH and γ-HCH in PUF disk versus SIP disk are attributed to lack of "comparability" of the PUF and SIP data sets, due to differences in effective air sampled by the two devices caused by saturation of these higher volatility compounds in the lower capacity PUF disk samplers. Analysis of PBDEs in PUF and SIP disks showed relatively good agreement but highlighted challenges associated with high blanks levels for PBDEs. The higher capacity SIP disk samplers allowed for the analysis of pentachlorobenzene (PeCBz) and hexachlorobenzene (HCBz) and revealed a relatively uniform global distribution of these compounds. The results of this study further validate the SIP disk sampler as a complement to the PUF disk sampler, with capabilities for a broad range of POPs targeted under international POPs treaties such as the Stockholm Convention on POPs and its Global Monitoring Plan.

Sources and fate of chiral organochlorine pesticides in western U.S. National Park ecosystems.

The enantiomer fractions (EFs) of alpha-hexachlorocyclohexane (α-HCH), cis-, trans-, and oxychlordane, and heptachlor epoxide were measured in 73 snow, fish, and sediment samples collected from remote lake catchments, over a wide range of latitudes, in seven western U.S. National Parks/Preserves to investigate their sources, fate, accumulation and biotransformation in these ecosystems. The present study is novel because these lakes had no inflow or outflow, and the measurement of chiral organochlorine pesticides (OCPs) EFs in snowpack from these lake catchments provided a better understanding of the OCP sources in the western United States, whereas their measurement in fish and sediment provided a better understanding of their biotic transformations within the lake catchments. Nonracemic α-HCH was measured in seasonal snowpack collected from continental U.S. National Parks, and racemic α-HCH was measured in seasonal snowpack collected from the Alaskan parks, suggesting the influence of regional sources to the continental U.S. parks and long-range sources to the Alaskan parks. The α-HCH EFs measured in trout collected from the lake catchments were similar to the α-HCH EFs measured in seasonal snowpack collected from the same lake catchments, suggesting that these fish did not biotransform α-HCH enantioselectively. Racemic cis-chlordane was measured in seasonal snowpack and sediment collected from Sequoia, indicating that it had not undergone significant enantioselective biotransformation in urban soils since its use as a termiticide in the surrounding urban areas. However, nonracemic cis-chlordane was measured in seasonal snowpack and sediments from the Rocky Mountains, suggesting that cis-chlordane does undergo enantioselective biotransformation in agricultural soils. The trout from these lakes showed preferential biotransformation of the (+)-enantiomer of cis-chlordane and the (-)-enantiomer of trans-chlordane.

Enantiomeric signatures of organochlorine pesticides in Asian, trans-Pacific, and western U.S. air masses.

The enantiomeric signatures of organochlorine pesticides were measured in air masses from Okinawa, Japan and three remote locations in the Pacific Northwestern United States: Cheeka Peak Observatory (CPO), a marine boundary layer site on the Olympic Peninsula of Washington at 500 m above sea level (m.a.s.l); Mary's Peak Observatory (MPO), a site at 1250 m.a.s.l in Oregon's Coast range; and Mt. Bachelor Observatory (MBO), a site at 2763 m.a.s.l in Oregon's Cascade range. The enantiomeric signatures of composite soil samples, collected from China, South Korea, and the western U.S. were also measured. The data from chiral analysis was expressed asthe enantiomeric fraction, defined as (+) enantiomer/(sum of the (+) and (-) enantiomers), where a racemic composition has EF = 0.5. Racemic alpha-hexachlorocyclohexane (alpha-HCH) was measured in Asian air masses at Okinawa and in Chinese and South Korean soils. Nonracemic alpha-HCH (EF = 0.528 +/- 0.0048) was measured in regional air masses at CPO, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the alpha-HCH EFs were significantly more racemic (EF = 0.513 +/- 0.0003, p < 0.001). Racemic alpha-HCH was consistently measured at MPO and MBO in trans-Pacific air masses that had spent considerable time in the free troposphere. The alpha-HCH EFs in CPO, MPO, and MBO air masses were negatively correlated (p = 0.0017) with the amount of time the air mass spent above the boundary layer, along the 10-day back air mass trajectory, prior to being sampled. This suggests that, on the West coast of the U.S., the alpha-HCH in the free troposphere is racemic. Racemic signatures of cis- and trans-chlordane were measured in air masses at all four air sampling sites, suggesting that Asian and U.S. urban areas continue to be sources of chlordane that has not yet been biotransformed.

Trans-Pacific and regional atmospheric transport of polycyclic aromatic hydrocarbons and pesticides in biomass burning emissions to western North America.

The trans-Pacific and regional North American atmospheric transport of polycyclic aromatic hydrocarbons (PAHs) and pesticides in biomass burning emissions was measured in air masses from April to September 2003 at two remote sites in western North America. Mary's Peak Observatory (MPO) is located in Oregon's Coast Range and Cheeka Peak Observatory (CPO) is located on the tip of the Olympic Peninsula in Washington State. During this time period, both remote sites were influenced by PAH and pesticide emissions from forest fires in Siberia and regional fires in Oregon and Washington State. Concurrent samples were taken at both sites on June 2 and August 4, 2003. On these dates, CPO had elevated gas phase PAH, alpha-hexachlorocyclohexane, and retene concentrations (p < 0.05) and MPO had elevated retene, particulate phase PAH, and levoglucosan concentrations due to trans-Pacific transport of emissions from fires in Siberia. In addition, during the April to September 2003 sampling period, CPO and MPO were influenced by emissions from regional fires that resulted in elevated levoglucosan, dacthal, endosulfan, and gas phase PAH concentrations. Burned and unburned forest soil samples collected from the regional forest fire area showed that 34-100% of the pesticide mass was lost from soil due to burning. These data suggest that the trans-Pacific and regional atmospheric transport of biomass burning emissions results in elevated PAH and pesticide concentrations in western North America. The elevated pesticide concentrations are likely due to re-emission of historically deposited pesticides from the soil and vegetation during the fire event.

Solvent selection for pressurized liquid extraction of polymeric sorbents used in air sampling.

Pressurized liquid extraction (PLE) was evaluated as a method for extracting semivolatile organic compounds (SOCs) from air sampling media, including quartz fiber filter (QFF), polyurethane foam (PUF), and a polystyrene divinyl benzene copolymer (XAD-2). Hansen solubility parameter plots were used to aid in the PLE solvent selection in order to both reduce coextraction of polyurethane and save time in evaluating solvent compatibility during the initial steps of method development. A PLE solvent composition of 75:25% hexane:acetone was chosen for PUF. The XAD-2 copolymer was not solubilized under the PLE conditions used. The average percent PLE recoveries (and percent relative standard deviations) of 63 SOCs, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine, amide, triazine, thiocarbamate, and phosphorothioate pesticides, were 76.7 (6.2), 79.3 (8.1), and 93.4 (2.9)% for the QFF, PUF, and XAD-2, respectively.