Desert pastoralists’ negative and positive effects on rare wildlife in the Gobi

In arid regions of the developing world, pastoralists and livestock commonly inhabit protected areas, resulting in human–wildlife conflict. Conflict is inextricably linked to the ecological processes shaping relationships between pastoralists and native herbivores and carnivores. To elucidate relationships underpinning human–wildlife conflict, we synthesized 15 years of ecological and ethnographic data from Ikh Nart Nature Reserve in Mongolia's Gobi steppe. The density of argali (Ovis ammon), the world's largest wild sheep, at Ikh Nart was among the highest in Mongolia, yet livestock were >90% of ungulate biomass and dogs >90% of large‐carnivore biomass. For argali, pastoral activities decreased food availability, increased mortality from dog predation, and potentially increased disease risk. Isotope analyses indicated that livestock accounted for >50% of the diet of the majority of gray wolves (Canis lupus) and up to 90% of diet in 25% of sampled wolves (n = 8). Livestock composed at least 96% of ungulate prey in the single wolf pack for which we collected species‐specific prey data. Interviews with pastoralists indicated that wolves annually killed 1–4% of Ikh Nart's livestock, and pastoralists killed wolves in retribution. Pastoralists reduced wolf survival by killing them, but their livestock were an abundant food source for wolves. Consequently, wolf density appeared to be largely decoupled from argali density, and pastoralists had indirect effects on argali that could be negative if pastoralists increased wolf density (apparent competition) or positive if pastoralists decreased wolf predation (apparent facilitation). Ikh Nart's argali population was stable despite these threats, but livestock are increasingly dominant numerically and functionally relative to argali. To support both native wildlife and pastoral livelihoods, we suggest training dogs to not kill argali, community insurance against livestock losses to wolves, reintroducing key native prey species to hotspots of human–wolf conflict, and developing incentives for pastoralists to reduce livestock density.     

Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening

Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Bioaccumulation of perfluoroalkyl acids in dairy cows in a naturally contaminated environment

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg^?1. Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF?<?1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from ?1.95 to ?1.15 day kg^?1 with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.     

High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden

In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist.     

GROUND-WATER RECHARGE THROUGH ACTWE SAND DUNES IN NORTHWESTERN NEVADA1

ABSTRACT: Most water-resouree investigations in semiarid basins of the Great Basin in western North America conclude that ground-water recharge from direct precipitation on the valley floor is negligible. However, many of these basins contain large areas covered by unvegetated, active sand dunes that may act as conduits for ground-water recharge. The potential for this previously undocumented recharge was investigated in an area covered by sand dunes in Desert Valley, northwestern Nevada, using a deep percolation model. The model uses daily measurements of precipitation and temperature th determine energy and moisture balances, from which estimates of long-term mean annual recharge are made. For the study area, the model calculated a mean annual recharge rate of as much as 1.3 inches per year, or 17 percent of the long-term mean precipitation. Model simulations also indicate that recharge would be virtually zero if the study area were covered by vegetation rather than dunes.