p65—measuring for perfluorinated chemicals in land-applied biosolids and plants

1
26 Abstracts / Reproductive Toxicology 33 (2012) 1–29 derived. Corresponding time-weighted water intake rates were estimated for each duration. The resulting calculated health based values for PFBS were 9 and 7 g/L for subchronic and chronic expo- sures, respectively. Like PFOA, PFOS has a long half-life in humans (more than 5 years) and the time necessary to reach steady-state conditions would be approximately 16–27 years. Therefore only a chronic RfD was derived. A corresponding time-weighted water intake rate was estimated resulting in a chronic health-based value for PFOS of 0.3 g/L. doi:10.1016/j.reprotox.2011.11.098 P65—Measuring for perfluorinated chemicals in land-applied biosolids and plants Kim Harris 1,2,3,4,, Kenneth Gunter 1,2,3,4 , Gerald Golubski 1,2,3,4 , Bradley Grams 1 , Christopher Lau 1,2,3,4 , Marc Mills 1,2,3,4 , Mark Strynar 1,2,3,4 , John Washington 1,2,3,4 , Shoji Nakayama 2 , Christo- pher Higgins 3 , Lakhwinder Hundal 4 1 US EPA-Region 5, Chicago, IL, United States 2 US EPA Research Triangle Park, NC, United States 3 Colorado School of Mines, Golden, CO, United States 4 Metropolitan Water Reclamation District of Greater Chicago, Chicago, IL, United States Perfluorinated chemicals (PFCs) consist of a diverse group of compounds characterized by their unique chemical–physical prop- erties. Because of their widespread use in industrial and consumer applications, PFCs eventually reach wastewater treatment plants (WWTPs) through industrial discharge, wastewaters generated by the cleaning of PFC-treated products, leaching of plastic products and indirect nonpoint sources. As such, WWTPs may be a major route of PFCs to the environment since conventional WWTPs have proven to be ineffective in removing PFCs, and under certain pro- cesses can increase concentrations. With respect to possible modes of human exposure and risk, several studies have shown significant concentrations of PFCs in generated WWTP sludge (biosolids). As such, there is concern for land application of biosolids since this commonly used waste disposal practice could present direct expo- sure routes through consumption of foods and crops. This concern has been highlighted recently by a contamination event in Decatur, Alabama, where elevated levels of PFCs were found and traced back to treated municipal biosolids that was applied to 4900 acres of rural land used for grazing cattle and crops. Although crops fertil- ized with PFC-containing biosolids may be an important exposure route to humans, few studies have attempted to estimate the trans- fer potential of PFCs from soil to plant. As little data exist regarding the levels of PFCs in soils after land application or plant uptake resulting from this practice, our study is designed to examine whether detectable levels of PFCs are found in soil and plants of areas where biosolids had been land applied as fertilizer generated from mixed industrial and domestic waste facilities. In addition, we will conduct a controlled study in the field to assess the uptake of PFC in a variety of plants grown in contaminated biosolids. doi:10.1016/j.reprotox.2011.11.099 P66—Perfluorophosphonic acids, polyfluoroalkyl phosphoric acids, and perfluoro-4-ethylcyclohexane sulfonate in Canadian rivers Amila O. De Silva 1,, Brian Scott 1 , Mark Sekela 2 , Melissa Gledhill 2 , Myriam Rondeau 2 , Sean Backus 2 , Derek Muir 1 1 Aquatic Ecosystem Protection Research Division, Ottawa, ON, Canada 2 Water Quality Monitoring and Surveillance, Environment Canada, Ottawa, ON, Canada Mono- and di-substituted polyfluoroalkyl phosphoric acid (mono- and di-PAPs) and perfluoroalkylphosphonic acids (PFPAs) are polyfluorinated chemicals that are used in to provide water and oil repellency in food-contact packaging, and as foam stabiliz- ers in personal care products and pesticide formulations. Previous studies indicated PAPs undergo metabolism and biodegradation to produce perfluorocarboxylates (PFCAs), suggesting PAPs may be a significant source of PFCA exposure. in humans. The PFPAs are a high production volume chemical (>4000 kg/y 1998–2002). PFPAs are resistant to degradation and are recalcitrant similar to the highly persistent perfluorocarboxylates (PFCAs). In 2006, the USEPA prohibited the use of PAPs and PFPAs in pesticide formulations used for food crops, indicating concern over these chemicals in the environment. Perfluoro-4-ethylcyclohexane sulfonate (PFECHS) is currently used as an abrasion inhibitor in aircraft hydraulic fluids, however, there is no data currently available on its environmental distribution. In order to gain an understanding of the distribution of these compounds in Canada, water was sampled from freshwater ecosystems. Analysis of di- PAPs ((OH)(O)P(OCH 2 CH 2 (CF 2 ) x,y F) 2 , where x and y = 4, 6, 8, or 10), PFECHS and PFPAs (F(CF 2 ) x P(O)(OH) 2 , where x = 6, 8, or 10) was performed using liquid chromatography–tandem mass spectrom- etry (LC–MS/MS) with quantification using authentic standards. Using measured flow rates at sampling stations permitted the cal- culation of mass flows of these chemicals. The 6:2 diPAP and C8 PFPA was detected in all samples with some contribution from longer and shorter chain length homologues. The highest con- centrations were observed in Wascana Creek (50 ng/L 6:2 diPAP, 2 ng/L C8 PFPA) in the province Saskatchewan at a site down- stream of a large wastewater treatment plant serving the city of Regina. Unline PFPAs and diPAPs, PFECHS was prevalent (1 ng/L) in the fast flowing St. Lawrence River at concentrations. Monthly

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Page 1: P65—Measuring for perfluorinated chemicals in land-applied biosolids and plants

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6 Abstracts / Reproductiv

erived. Corresponding time-weighted water intake rates werestimated for each duration. The resulting calculated health basedalues for PFBS were 9 and 7 �g/L for subchronic and chronic expo-ures, respectively.

Like PFOA, PFOS has a long half-life in humans (more than 5ears) and the time necessary to reach steady-state conditionsould be approximately 16–27 years. Therefore only a chronic RfDas derived. A corresponding time-weighted water intake rate was

stimated resulting in a chronic health-based value for PFOS of.3 �g/L.

oi:10.1016/j.reprotox.2011.11.098

65—Measuring for perfluorinated chemicals in land-appliediosolids and plants

im Harris 1,2,3,4,∗, Kenneth Gunter 1,2,3,4, Gerald Golubski 1,2,3,4,radley Grams 1, Christopher Lau 1,2,3,4, Marc Mills 1,2,3,4, Marktrynar 1,2,3,4, John Washington 1,2,3,4, Shoji Nakayama 2, Christo-her Higgins 3, Lakhwinder Hundal 4

US EPA-Region 5, Chicago, IL, United StatesUS EPA Research Triangle Park, NC, United StatesColorado School of Mines, Golden, CO, United StatesMetropolitan Water Reclamation District of Greater Chicago,hicago, IL, United States

Perfluorinated chemicals (PFCs) consist of a diverse group ofompounds characterized by their unique chemical–physical prop-rties. Because of their widespread use in industrial and consumerpplications, PFCs eventually reach wastewater treatment plantsWWTPs) through industrial discharge, wastewaters generated byhe cleaning of PFC-treated products, leaching of plastic productsnd indirect nonpoint sources. As such, WWTPs may be a majoroute of PFCs to the environment since conventional WWTPs haveroven to be ineffective in removing PFCs, and under certain pro-esses can increase concentrations. With respect to possible modesf human exposure and risk, several studies have shown significantoncentrations of PFCs in generated WWTP sludge (biosolids). Asuch, there is concern for land application of biosolids since thisommonly used waste disposal practice could present direct expo-ure routes through consumption of foods and crops. This concernas been highlighted recently by a contamination event in Decatur,labama, where elevated levels of PFCs were found and traced back

o treated municipal biosolids that was applied to 4900 acres ofural land used for grazing cattle and crops. Although crops fertil-zed with PFC-containing biosolids may be an important exposureoute to humans, few studies have attempted to estimate the trans-er potential of PFCs from soil to plant.

As little data exist regarding the levels of PFCs in soils after landpplication or plant uptake resulting from this practice, our studys designed to examine whether detectable levels of PFCs are foundn soil and plants of areas where biosolids had been land applieds fertilizer generated from mixed industrial and domestic wasteacilities. In addition, we will conduct a controlled study in the

eld to assess the uptake of PFC in a variety of plants grown inontaminated biosolids.

oi:10.1016/j.reprotox.2011.11.099

cology 33 (2012) 1–29

P66—Perfluorophosphonic acids, polyfluoroalkyl phosphoricacids, and perfluoro-4-ethylcyclohexane sulfonate in Canadianrivers

Amila O. De Silva 1,∗, Brian Scott 1, Mark Sekela 2, Melissa Gledhill 2,Myriam Rondeau 2, Sean Backus 2, Derek Muir 1

1 Aquatic Ecosystem Protection Research Division, Ottawa, ON, Canada2 Water Quality Monitoring and Surveillance, Environment Canada,Ottawa, ON, Canada

Mono- and di-substituted polyfluoroalkyl phosphoric acid(mono- and di-PAPs) and perfluoroalkylphosphonic acids (PFPAs)are polyfluorinated chemicals that are used in to provide waterand oil repellency in food-contact packaging, and as foam stabiliz-ers in personal care products and pesticide formulations. Previousstudies indicated PAPs undergo metabolism and biodegradation toproduce perfluorocarboxylates (PFCAs), suggesting PAPs may be asignificant source of PFCA exposure.

in humans. The PFPAs are a high production volume chemical(>4000 kg/y 1998–2002). PFPAs are resistant to degradation and arerecalcitrant similar to the highly persistent perfluorocarboxylates(PFCAs). In 2006, the USEPA prohibited the use of PAPs and PFPAs inpesticide formulations used for food crops, indicating concern overthese chemicals in the environment. Perfluoro-4-ethylcyclohexanesulfonate (PFECHS) is currently used as an abrasion inhibitorin aircraft hydraulic fluids, however, there is no data currentlyavailable on its environmental distribution. In order to gain anunderstanding of the distribution of these compounds in Canada,water was sampled from freshwater ecosystems. Analysis of di-PAPs ((OH)(O)P(OCH2CH2(CF2)x,yF)2, where x and y = 4, 6, 8, or 10),PFECHS and PFPAs (F(CF2)xP(O)(OH)2, where x = 6, 8, or 10) wasperformed using liquid chromatography–tandem mass spectrom-etry (LC–MS/MS) with quantification using authentic standards.Using measured flow rates at sampling stations permitted the cal-culation of mass flows of these chemicals. The 6:2 diPAP and C8PFPA was detected in all samples with some contribution fromlonger and shorter chain length homologues. The highest con-centrations were observed in Wascana Creek (50 ng/L 6:2 diPAP,

2 ng/L C8 PFPA) in the province Saskatchewan at a site down-stream of a large wastewater treatment plant serving the city ofRegina. Unline PFPAs and diPAPs, PFECHS was prevalent (1 ng/L)in the fast flowing St. Lawrence River at concentrations. Monthly