Significant Residual Fluoroalcohols Present in Various Fluorinated Materials

Polyfluorinated telomer alcohols and sulfonamides are classes of compounds recently identified as precursor molecules to the perfluorinated acids detected in the environment. Despite the detection and quantification of these volatile compounds in the atmosphere, their sources remain unknown. Both classes of compounds are used in the synthesis of various fluorosurfactants and incorporated in polymeric materials used extensively in the carpet, textile, and paper industries. This study has identified the presence of residual unbound fluoro telomer alcohols (FTOHs) in varying chain lengths (C6−C14) in several commercially available and industrially applied polymeric and surfactant materials. NMeFOSE, a perfluoroalkyl sulfonamido alcohol, was also detected in a commercially available carpet protector product. A method was developed to remove these residual compounds from polymeric and surfactant materials by dispersion in water and stripping of the volatiles using a constant flow of air and trapping on XAD resin. Using gas chromatography mass spectrometry analysis, it was determined that the fluorinated materials examined consist of 0.04−3.8% residual alcohols on a fluoro alcohol to dry mass basis. These values indicate that residual alcohols, left unreacted and unbound from the manufacturing process of fluorinated polymers and surfactants, could be a significant source of the polyfluorinated telomer alcohols and sulfonamides released into the environment. This study suggests that elimination or reduction of these residual alcohols from all marketed fluorinated polymers and fluorosurfactants is key in reducing the prevalence of perfluorinated acids formed in the environment

Microbial Oxidation of 1,2-Dichloroethane under Anoxic Conditions with Nitrate as Electron Acceptor in Mixed and Pure Cultures

Many organisms have been found to readily oxidize the prevalent contaminant 1,2-dichloroethane (1,2-DCA) to CO2 under aerobic conditions. Some organisms have also been isolated that can reduce 1,2-DCA to ethene via dihaloelimination under anaerobic, fermentative conditions. However, none have been described that can metabolize 1,2-DCA under anoxic, nitrate-reducing conditions. In microcosms prepared from aquifer material and groundwater samples from a contaminated site in eastern Louisiana, USA, 1,2-DCA was observed to degrade with nitrate as the terminal electron acceptor. Nitrate-dependent enrichment cultures were developed from these microcosms that sustained rapid 1,2-DCA degradation rates of up to 500 μM day−1. This degradation was tightly coupled to complete reduction of nitrate via nitrite to nitrogen gas. A novel 1,2-DCA-degrading organism belonging to the Betaproteobacteria (affiliated with the genus Thauera) was isolated from this enrichment culture. However, degradation rates were much slower in cultures of the isolate than observed in the parent mixed culture. Complete mineralization of 1,2-DCA to CO2 was linked to cell growth and to nitrate reduction in both enrichment and isolated cultures. Monochloroacetate, a putative metabolite of 1,2-DCA degradation, could also be mineralized by these cultures

Fluorotelomer Acids are More Toxic Than Perfluorinated Acids

Saturated and unsaturated fluorotelomer carboxylic acids have been identified as intermediates in the degradation of fluorotelomer alcohols to perfluorinated carboxylic acids (PFCAs). Although surface waters are the likely environmental sink for telomer acids, no fate or toxicity data exist for this matrix. We assessed the acute toxicity of the 4:2, 6:2, 8:2, and 10:2 saturated (FTCA) and unsaturated (FTUCA) fluorotelomer carboxylic acids to Daphnia magna, Chironomus tentans, and Lemna gibba. In general, toxicity increased with increasing fluorocarbon (FC) chain length, particularly for telomer acids of ≥8 FCs. In addition, the FTCAs were generally more toxic than the corresponding FTUCAs. Acute EC50s ranged from 0.025 mg/L (0.04 μmol/L) for D. magna (10:2 FTCA, immobility) to 63 mg/L (167 μmol/L) for C. tentans (6:2 FTCA, growth). While chain-length trends observed in the current study agree with those previously reported for PFCAs, the toxicity thresholds generated here are up to 10 000 times smaller. Our data provide the first evidence that PFCA precursors are more toxic than the PFCAs themselves

Isotope Analysis As a Natural Reaction Probe to Determine Mechanisms of Biodegradation of 1,2-Dichloroethane

1,2-Dichloroethane (1,2-DCA), a chlorinated aliphatic hydrocarbon, is a well-known groundwater contaminant. In this study, fractionation of stable carbon isotope values of 1,2-DCA during biodegradation was used as a novel reaction probe to provide information about the mechanism of 1,2-DCA biodegradation under both aerobic (O2-reducing) and anaerobic (NO3-reducing) conditions. Under O2-reducing conditions, an isotopic enrichment value ( ε) of −25.8 ± 1.1‰ (±95% confidence intervals) was measured for the enrichment culture. Under NO3-reducing conditions, an ε-value of −25.8 ± 3.5‰ was measured. The microbial culture produced isotopic enrichment values ( ε) that are not only large and reproducible, but also are the same whether O2 or NO3 was used as an electron acceptor. Combining data measured under both O2- and NO3-reducing conditions, an isotopic enrichment value ( ε) of −25.8 ± 1.6‰ is measured for the microbial culture during 1,2-DCA degradation. The ε-value can be converted into a kinetic isotope effect (KIE) value to relate the observed isotopic fractionation to the mechanism of degradation. This KIE value (1.05) is consistent with degradation via hydrolytic dehalogenation under both electron-accepting conditions. This study demonstrates the added value of compound-specific isotope analysis not only as a technique to verify the occurrence and extent of biodegradation in the field, but also as a natural reaction probe to provide insight into the enzymatic mechanism of contaminant degradation

Pathway Dependent Isotopic Fractionation during Aerobic Biodegradation of 1,2-Dichloroethane

1,2-Dichloroethane (1,2-DCA) is a widespread groundwater contaminant known to be biodegradable under aerobic conditions via enzymatic oxidation or hydrolytic dehalogenation reactions. Current literature reports that stable carbon isotope fractionation of 1,2-DCA during aerobic biodegradation is large and reproducible (−27 to −33‰). In this study, a significant variation in the magnitude of stable carbon isotope fractionation during aerobic biodegradation was observed. Biodegradation in experiments involving microcosms, enrichment cultures, and pure microbial cultures produced a consistent bimodal distribution of enrichment factors (ε) with one mean ε centered on −3.9 ± 0.6‰ and the other on −29.2 ± 1.9‰. Reevaluation of ε in terms of kinetic isotope effects 12k/13k gave values of 12k/13k = 1.01 and 1.06, which are typical of oxidation and hydrolytic dehalogenation (SN2) reactions, respectively. The bimodal distribution is therefore consistent with the microbial degradation of 1,2-DCA by two separate enzymatic pathways. This interpretation is further supported in this study by experiments with pure strains of Xanthobacter autotrophicus GJ10, Ancylobacter aquaticus AD20, and Pseudomonas sp. Strain DCA1 for which the enzymatic degradation pathways are well-known. A small fractionation of −3.0‰ was measured for 1,2-DCA degradation by Pseudomonas sp. Strain DCA1 (monooxygenase enzyme), while degradation by the hydrolytic dehalogenase enzyme by the other two pure strains was characterized by fractionation of −32.3‰