Per- and polyfluoroalkyl substances in source and treated drinking waters of the United States.

Contaminants of emerging concern (CECs), including per- and polyfluoroalkyl substances (PFAS), are of interest to regulators, water treatment utilities, the general public and scientists. This study measured 17 PFAS in source and treated water from 25 drinking water treatment plants (DWTPs) as part of a broader study of CECs in drinking water across the United States. PFAS were quantitatively detected in all 50 samples, with summed concentrations of the 17 PFAS ranging from <1 ng/L to 1102 ng/L. The median total PFAS concentration was 21.4 ng/L in the source water and 19.5 ng/L in the treated drinking water. Comparing the total PFAS concentration in source and treated water at each location, only five locations demonstrated statistically significant differences (i.e. P < 0.05) between the source and treated water. When the perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) concentrations in the treated drinking water are compared to the existing US Environmental Protection Agency's PFOA and PFOS drinking water heath advisory of 70 ng/L for each chemical or their sum one DWTP exceeded the threshold. Six of the 25 DWTPs were along two large rivers. The DWTPs within each of the river systems had specific PFAS profiles, with the three DWTPs from one river being dominated by PFOA, while three DWTPs on the second river were dominated by perfluorobutyric acid (PFBA).

A method for the analysis of perfluorinated compounds in environmental and drinking waters and the determination of their lowest concentration minimal reporting levels.

A trace analytical method was developed for the determination of seventeen specific perfluorinated chemicals (PFCs) in environmental and drinking waters. The objectives were to optimize an isotope-dilution method to increase the precision and accuracy of the analysis of the PFCs and to eliminate the need for matrix-matched standards. A 250 mL sample of environmental or drinking water was buffered to a pH of 4, spiked with labeled surrogate standards, extracted through solid phase extraction cartridges, and eluted with ammonium hydroxide in methyl tert-butyl ether: methanol solution. The sample eluents were concentrated to volume and analyzed by liquid chromatography/tandem mass spectrometry (LC-MS/MS). The lowest concentration minimal reporting levels (LCMRLs) for the seventeen PFCs were calculated and ranged from 0.034 to 0.600 ng/L for surface water and from 0.033 to 0.640 ng/L for drinking water. The relative standard deviations (RSDs) for all compounds were <20% for all concentrations above the LCMRL. The method proved effective and cost efficient and addressed the problems with the recovery of perfluorobutanoic acid (PFBA) and other short chain PFCs. Various surface water and drinking water samples were used during method development to optimize this method. The method was used to evaluate samples from the Mississippi River at New Orleans and drinking water samples from a private residence in that same city. The method was also used to determine PFC contamination in well water samples from a fire training area where perfluorinated foams were used in training to extinguish fires.

Polychlorinated dibenzo-p-dioxins and dibenzofurans in the atmosphere around the Great Lakes.

The atmospheric concentrations of PCDDs and PCDFs were measured in four sites near the shores of the North American Great Lakes. The sites included an urban site (Chicago, Illinois) and three rural/remote sites (Eagle Harbor, Michigan; Sleeping Bear Dunes, Michigan; and Sturgeon Point, New York). Sampling occurred every 24 days between November 2004 and December 2007. The concentration of PCDD/Fs averaged 2.3 +/- 0.2 fg WHO TEQ/m3 at Eagle Harbor, 35 +/- 3 fg WHO TEO/ m3 at Chicago, 7.4 +/- 1.4 fg WHO TEO/m3 at Sleeping Bear Dunes, and 13 +/- 2 fg WHO TED/m3 at Sturgeon Point. The total concentration of the 17 toxic PCDD/F congeners showed a significant seasonal trend at all sites, except Chicago. The date of maximum concentration averaged Dec 6 +/- 35 days, which is consistent with residential heating being an important source of PCDD/Fs to the atmosphere. A significant positive relationship between the logarithm of the total concentration of the 17 toxic PCDD/F congeners and the logarithm of the number of people within a 25 km radius around the sampling site was found. We suggest that urban and industrial areas, which are heavily populated, act as sources of PCDDs and PCDFs to the atmosphere.

Oxidation of selected organophosphate pesticides during chlorination of simulated drinking water.

Ten organophosphate (OP) pesticides: phorate, disulfoton, terbufos, methidathion, bensulide, chlorethoxyfos, phosmet, methyl parathion, phostebupirim, and temephos were evaluated for their potential to undergo oxidation to their respective oxons and/or other oxidation analogues in laboratory water. Samples were collected at time intervals up to 72h of chlorination and analyzed by both gas chromatography-mass selective detection (GC-MSD) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results show that methidathion and methyl parathion were stable in unchlorinated water, while all other OP pesticides were not stable over the 72h exposure period. In chlorinated water, phorate and disulfoton formed stable sulfone oxons. Temephos formed stable dioxon sulfoxide and dioxon sulfone. Methidathion, bensulide, chlorethyoxyfos, methyl parathion, and phostebupirim formed stable oxons over the 72h exposure period. Terbufos, phorate, disulfoton and temephos oxon sulfoxides; temephos sulfoxide; and phosmet oxon were initially formed but were not detected after 24h. The data illustrate that organothiophosphate pesticides may form oxons and/or other oxidation analogues during chlorination in water treatment plants, which are persistent for at least 72h.

Developmental toxicity in white leghorn chickens following in ovo exposure to perfluorooctane sulfonate (PFOS).

Studies show that perfluorinated compounds cause various toxicological effects; nevertheless, effects on immune function and developmental endpoints have not been addressed at length. This study examined the effects of perfluorooctane sulfonate (PFOS) in white leghorn hatchlings on various developmental, immunological, and clinical health parameters. In addition, serum PFOS concentrations were determined by LC/MS/MS. Embryonic day (ED) 0 eggs were injected with either safflower oil/10% DMSO (control, 0mg/kg egg wt) or PFOS in safflower oil/10% DMSO at 1, 2.5, or 5mg/kg egg wt, and the chicks were grown to post-hatch day (PHD) 14. Treatment with PFOS did not affect hatch rate. Following in ovo exposure chicks exhibited increases in spleen mass at all treatment levels, in liver mass at 2.5 and 5mg/kg egg wt, and in body length (crown-rump length) at the 5mg/kg treatment. Right wings were shorter in all treatments compared to control. Increases in the frequency of brain asymmetry were evident in all treatment groups. SRBC-specific immunoglobulin (IgM and IgY combined) titers were decreased significantly at all treatment levels, while plasma lysozyme activity was increased at all treatment levels. The PHA skin test response decreased in relation to increasing PFOS dose. Serum concentrations where significant immunological, morphological, and neurological effects were observed at the lowest dose (1mg/kg egg wt) averaged 154 ng PFOS/g serum. These concentrations fall within environmental ranges reported in blood samples from wild caught avian species; thereby, verifying that the environmental egg concentrations used for the injections do indeed relate to serum levels in hatchlings that are also environmentally relevant. These data indicate that immune alterations and brain asymmetry can occur in birds following in ovo exposure to environmentally relevant concentrations of PFOS and demonstrates the need for further research on the developmental effects of perfluorinated compounds in various species.

A general indication of the Contemporary background levels of PCDDs, PCDFs, and coplanar PCBs in the ambient air over rural and remote areas of the United States.

Long-term measurements of the atmospheric concentrations of PCDDs, PCDFs, and coplanar PCBs were taken in rural and remote areas of the United States by the National Dioxin Air Monitoring Network (NDAMN). A total of 21 quarterly sampling moments occurred from June, 1998 to December, 2002 at 34 locations geographically distributed throughout the United States. Sampling sites were located in rural and remote areas to obtain background air concentrations of dioxin-like compounds. Results were reported as the toxic equivalent (TEQ) of the mix of PCDDs/ PCDFs (TEQDF) and the mix of coplanar PCBs (TEQPCB). At the studied rural sites the mean annual TEQDF for each of the NDAMN sampling years was 10.43, 11.39, 10.40, and 10.47 fg m(-3) for 1999, 2000, 2001, and 2002, respectively. There was no statistically significant difference in the rural mean TEQDF air concentrations across the sampling years (at 0.05 level of significance), although the mean concentration in sampling year 2000 increased 10% relative to the other sampling years. The 95th percent confidence interval of TEQDF air concentrations in rural areas of the United States is from 6.4 to 15.4 fg m(-3), indicating there is a 95% probability that the true mean falls within this range. Mean annual atmospheric concentrations (TEQDF) at the remote sites were 1.41, 0.99, 0.7, and 1.07 fg m(-3) in 1999, 2000, 2001, and 2002, respectively, The 95th percent confidence interval of TEQDF air concentrations suggest that the true mean annual atmospheric TEQDF concentration in remote areas of the United States is between 0.1 and 3 fg m(-3). The remote sites have average air TEQDF concentrations that are approximately 10 times lower than those of the rural sites. For the rural sites, there was close agreement in the mean annual air concentrations of coplanar PCBs (TEQPCB) among the years 1999, 2000, 2001, and 2002 (i.e., 0.62, 0.69, 0.59, and 0.7 fg m(-3), respectively). However, as is the case with PCDDs/PCDFs, there was a marked increase (i.e., approximately equal to 13%) in the annual rural mean air concentration in 2000 as compared to the other sampling years. The confidence intervals across the NDAMN sampling years suggests a 95% probability that mean TEQPcB atmospheric concentrations in rural and remote areas of the United States are within the range of 0.5-0.9 fg m(-3) and 0.1-0.5 fg m(-3), respectively. The congener distributional patterns of PCDDs/PCDFs in air were relatively constant at all locations, and match the profile of urban air. We propose the hypothesis that urban areas are regional sources of PCDDs/PCDFs and are affecting atmospheric levels in rural and remote areas of the United States.

Concentrations of polychlorinated dibenzo-p-dioxins in processed ball clay from the United States.

Processed ball clays commonly used by the ceramic art industry in the United States were collected from retail suppliers and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs). The average PCDD toxic equivalent (TEQ) concentrations of these processed ball clays was approximately 800 pg/g (TEQ-WHO) with characteristic congener profiles and isomer distributions similar to patterns of previously analyzed raw and processed ball clays. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. Correlation analyses reveal no significant relationship between total organic carbon (TOC) and either individual, homologues, and total tetra-through octa-chlorinated PCDD congeners, or TEQ concentrations of the processed ball clays. The results are consistent with earlier studies on levels of PCDDs in ball clays. Data from earlier studies indicated that dioxins may be released to the environment during the processing of raw clay or the firing process used in commercial ceramic facilities. The presence of dioxin in the clays also raises concerns about potential occupational exposure for individuals involved in the mining/processing of ball clay, ceramics manufacturing and ceramic artwork.

Survey of dioxin-like compounds in dairy feeds in the United States.

The United States Environmental Protection Agency (USEPA) has completed a survey of dioxin-like compounds (including 17 dioxin and furan (CDD/F) congeners and 12 coplanar polychlorinated biphenyl (PCBs) congeners) in dairy feeds from 10 dairy research facilities around the United States, sampling the overall mixtures and the major and minor feed components. Low levels of dioxin were found in all feed mixtures with an average concentration of 0.05 pg/g (ppt) toxic equivalent (TEQ) dry weight. This is lower than previously found in dairy feeds by about a factor of 4. While it is possible that generally lower levels of dioxins in the environment in recent years may explain this result, examinations of the data suggest that the oven drying used to prepare the wet feed samples could have resulted in a loss of dioxins from the feed materials. The percentage of the total TEQ due to CDD/Fs was about four times that of PCBs. Leafy vegetations in the feed (the silages and the hays) had concentrations about twice as high as nonleafy, protected vegetation of the feeds (the ground or meal corn, cottonseed, and others). Minor components did not significantly influence the final feed mixture concentration of dioxin TEQ. However, in one of the feed mixtures, a minor component with a high concentration of 38.5 ppt TEQ effectively doubled the concentration of the overall feed mixture.

Dibenzo-p-dioxins in the environment from ceramics and pottery produced from ball clay mined in the United States.

Processed ball clay samples used in the production of ceramics and samples of the ceramic products were collected and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs). The processed ball clay had average PCDD concentrations of 3.2 ng/g toxic equivalents, a congener profile, and isomer distribution consistent with those found previously in raw ball clay. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. The final fired ceramic products were found to be free of PCDDs/PCDFs at the LODs. A consideration of the conditions involved in the firing process suggests that the PCDDs, if not destroyed, may be released to the atmosphere and could represent an as yet unidentified source of dioxins to the environment. In addition, the PCDDs in clay dust generated during manufacturing operations may represent a potential occupational exposure.

Investigation of polychlorinated dibenzo-p-dioxins, dibenzo-p-furans and selected coplanar biphenyls in Scottish farmed Atlantic salmon (Salmo salar).

Farmed and wild Scottish Atlantic salmon were obtained from retail suppliers, producers, and Stirling University in Scotland during January, 1999, for determination of 17 2,3,7,8-C1-substituted PCDDs and PCDFs, and seven nonortho- and mono-ortho-PCBs. The study confirms previous reports of relatively high concentrations of PCDDs, PCDFs and, especially, PCBs in farmed Scottish salmon. The results indicate that high consumption of salmon, particularly by children under 5 years, could lead to intakes above the tolerable daily intake (TDI) and tolerable weekly intake (TWI) for these chemicals, especially the PCBs, when combined with mean or high level intakes from the typical UK diet. These results suggest further investigation of farmed salmon and salmon feed, including feed fortified with fish oil and feed fortified with selected vegetable oils, is warranted.