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 Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company.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.     

Dietary exposure to polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls of the French population: Results of the second French Total Diet Study

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) bioaccumulate through the food chain and are therefore of public health concern. Exposure to these compounds was assessed in the second French Total Diet Study (TDS). Food samples (n=583) were collected to be representative of the whole diet of the population, prepared as consumed, and analyzed. Contamination data were combined with national individual food consumption data. Mean exposure (95th percentile) to PCDD/F+DL-PCBs was assessed to be 0.57 (1.29) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the adult population and 0.89 (2.02) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the child and teenager population. Less than 4% of the population exceeded the health-based guidance value for PCDD/F+DL-PCBs. Mean exposure (95th percentile) to the six indicator PCBs (PCB 28, 52, 101, 138, 153, 180) was estimated at 2.71 (7.90) ng (kg bw)(-1) d(-1) in the adult population and 3.77 (11.7) ng (kg bw)(-1) d(-1) in the child and teenager population. Only 2.6% of the adults [CI(95%): 1.9; 3.3] and 6.5% of the children and teenagers [5.2; 7.8] exceeded the health-based guidance value for total PCBs. These results show that the contamination levels in food and therefore the exposure of the general French population to PCDD/Fs and PCBs have declined (by a factor of 3.2 for PCDD/F+DL-PCBs and about three for total PCBs) since the last evaluation, which was conducted using another methodology in 2005 and 2007, and show the efficiency of the European risk management measures which came into force after these evaluations.     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

Quantification of ionophores in aged poultry litter using liquid chromatography tandem mass spectrometry

Veterinary anticoccidials, biochemically known as ionophores, are widely used in poultry feed at therapeutic levels to treat Coccidiosis and at sub-therapeutic levels for growth- promotion. Commonly used ionophores in the US poultry industry are monensin, salinomycin, lasalocid and narasin. There is an increasing concern regarding the persistence of these anticoccidials in the environment. However, little attention has been directed to methods development for quantitatively measuring ionophores in complex environmental matrices such as poultry litters that are land applied. Here, we describe a rapid and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS)-based method developed for simultaneous quantification of monensin, lasalocid, salinomycin, and narasin in aged poultry litter samples. Results show significant level of monensin (97.8 ± 3.2?μg kg(-1)), lasalocid (19.2 ± 6.6?μg kg(-1)), salinomycin (70 ± 2.7?μg kg(-1)) and narasin (57.3 ± 2.6?μg kg(-1)) in poultry litter stored for over three years at < 5°C. Our findings indicate that even after several years of unmanaged storage of poultry litter, ionophores may continue to persist in this matrix, raising the possibility of prolonged release into the environment.     

Optimization of photo-Fenton process parameters on carbofuran degradation using central composite design

Carbofuran, one of the most toxic and biorefractory carbamate compounds, is widely used in insecticides in Taiwan (9-18% of total insecticides production per year). In the present study, a central composite design experiment was used to study the effect of photo-Fenton treatment on carbofuran solution and to optimize the process variables such as carbofuran concentration (1-100 mg L(-1)), H(2)O(2) dosage rate (0.25-6 mg L(-1) min(-1)) and Fe(3+) dosage (1-50 mg L(-1)), which influenced the efficiency of carbofuran degradation and mineralization. The results indicated that all the variables investigated in this study had significant roles in the degradation and mineralization of carbofuran in solution. The carbofuran degradation and mineralization efficiencies were increased with increase in H(2)O(2) dosage rate and Fe(3+) dosage, and with decrease in carbofuran concentration. Furthermore, optimum values of both H(2)O(2) dosage rate and Fe(3+) dosage were found to shift to higher values as carbofuran concentration increased. Based on the model obtained in this study, optimum H(2)O(2) dosage rate and Fe(3+) dosage were found to be 4 mg L(-1) min(-1) and 20 mg L(-1), respectively, for 51 mg L(-1) of carbofuran concentration. Under these conditions, carbofuran was completely removed within 30 min and coupled with 78% mineralization at the end of experiment.     

Detecting diclofenac in livestock carcasses in India with an ELISA: a tool to prevent widespread vulture poisoning

Diclofenac, a non-steroidal anti-inflammatory drug (NSAID), has caused catastrophic vulture declines across the Indian sub-continent. Here, an indirect ELISA is used to detect and quantify diclofenac in 1251 liver samples from livestock carcasses collected across India between August 2007 and June 2008, one to two years after a ban on diclofenac manufacture and distribution for veterinary use was implemented. The ELISAs applicability was authenticated with independent data obtained using LC-ESI/MS. Of 1251 samples, 1150 (91.9%) were negative for diclofenac using both methods, and 60 (4.8%) were positive at 10-4348 and 10-4441 μg kg(-1) when analysed by ELISA and LC-ESI/MS, respectively. The residue level relationship in the 60 positive samples was highly significant (p < 0.001, r(2) = 0.644). Data suggest that this immunological assay could be used not only for cost effective sample screening, but also for residue level semi-quantification.     

Mycoremediation—a prospective environmental friendly technique of bioseparation and dewatering of domestic wastewater sludge

INTRODUCTION: Environmental safe and friendly management and disposal of wastewater sludge is a problem of every treatment plant throughout the world. Bioseparation and dewaterability of raw domestic wastewater sludge were evaluated for proper management and disposal by mycoremediation, i.e., using prior grown 2% (v/v) spore suspension of filamentous fungal (Mucor hiemalis Wehmer) broth inoculation, which were grown in 2% (w/v) solution of malt extract and wheat flour for 48-60 h in orbital shaker. DISCUSSION: Within 2-3 days of treatment application, encouraging results were achieved in total dry solids (TDS), total suspended solid (TSS), turbidity, chemical oxygen demand (COD), specific resistance to filtration (SRF), and pH due to fungal treatment in recognition of bioseparation and dewaterability of wastewater sludge compared to control. The significant reduction of TDS was remarked at fungal biomass (FB) in wheat flour (WF) treatment. The removal of TSS, turbidity, COD, and SRF were observed 96.0%, 99.4%, 92.6%, and 97.6%, respectively, in supernatant at 5 days by FB in WF. The SRF measuring the dewaterability was decreased with maximum (0.26 × 10(-12) mg/kg) equivalent to 95.5% at 2 days in FB in WF also. FB in WF broth is a potential, environmental friendly, comparatively low-cost biological technique which might play the significant role for bioremediation and bioseparation of domestic wastewater sludge. The present technique may bring a dynamic change in treatment of wastewater in future.     

Genotoxicity associated with oxidative damage in the liver and kidney of mice exposed to dimethoate subchronic intoxication

Background and aims  

Because of the widespread use of pesticides for domestic and industrial applications, the evaluation of their toxic effects is of major concern to public health. The aim of the present study was to investigate the propensity of dimethoate (DM), an organophosphorus pesticide, to cause oxidative damage in the liver and kidney of mice and its associated genotoxic effect.     

Natural attenuation is enhanced in previously contaminated and coniferous forest soils

Purpose  

Prevalence of organic pollutants or their natural analogs in soil is often assumed to lead to adaptation in the bacterial community, which results in enhanced bioremediation if the soil is later contaminated. In this study, the effects of soil type and contamination history on diesel oil degradation and bacterial adaptation were studied.