Fluorotelomer polymers are used in a broad array of products in modern societies worldwide and, if they degrade at significant rates, potentially are a significant source of perfluorooctanoic acid (PFOA) and related compounds to the environment To evaluate this possibility, we incubated an acrylate-linked fluorotelomer polymer in soil microcosms and monitored the microcosms for possible fluorotelomer (FT) and perfluorinated-compound (PFC) degradation products using GC/MS and LC/MS/MS. This polymer scavenged FTs and PFCs aggressively necessitating development of a multistep extraction using two solvents. Aged microcosms accumulated more FTs and PFCs than were present in the fresh polymer indicating polymer degradation with a half-life of about 870-1400 years for our coarse-grained test polymer. Modeling indicates that more-finely grained polymers in soils might have half-lives of about 10-17 years assuming degradation is surface-mediated. In our polymer-soil microcosms, PFOA evidently was lost with a half-life as short as 130 days, possibly by polymer-catalyzed degradation. These results suggest that fluoratelomer-polymer degradation is a significant source of PFOA and other fluorinated compounds to the environment.
Agricultural practices are increasingly incorporating recycled waste materials, such as biosolids, to provide plant nutrients and enhance soil functions. Although biosolids provide benefits to soil, municipal wastewater treatment plants receive pharmaceuticals and heavy metals that can accumulate in biosolids, and land application of biosolids can transfer these contaminants to the soil. Environmental exposure of these contaminants may adversely affect wildlife, disrupt microbial communities, detrimentally affect human health through long-term exposure, and cause the proliferation of antibiotic-resistant bacteria. This study considers the use of biochar co-amendments as sorbents for contaminants from biosolids. The sorption of pharmaceuticals (ciprofloxacin, triclocarban, triclosan), and heavy metals (Cu, Cd, Ni, Pb) to biochars and biochar-biosolids-soil mixtures was examined. Phenylurea herbicide (monuron, diuron, linuron) sorption was also studied to determine the potential effect of biochar on soil-applied herbicides. A softwood (SW) biochar (510°C) and a walnut shell (WN) biochar (900°C) were used as contrasting biochars to highlight potential differences in biochar reactivity. Kaolinite and activated carbon served as mineral and organic controls. Greater sorption for almost all contaminants was observed with WN biochar over SW biochar. The addition of biosolids decreased sorption of herbicides to SW biochar, whereas there was no observable change with WN biochar. The WN biochar showed potential for reducing agrochemical and contaminant transport but may inhibit the efficacy of soil-applied herbicides. This study provides support for minimizing contaminant mobility from biosolids using biochar as a co-amendment and highlights the importance of tailoring biochars for specific characteristics through feedstock selection and pyrolysis-gasification conditions.
Animal waste products from concentrated animal feeding operations are a significant source of antibiotics to the environment. Monensin, an ionophore antibiotic commonly used to increase feed efficiency in livestock, is known to have varied toxicological effects on nontarget species. The current study builds on prior studies evaluating the impact of dairy management on groundwater quality by examining the transport of monensin in an agricultural field with coarse-textured soils during irrigation with lagoon wastewater. The dairy is located in California's San Joaquin Valley, where groundwater can be encountered <5 m below the surface. Groundwater samples were collected from a network of monitoring wells installed throughout the dairy and adjacent to irrigated fields before and after an irrigation event, which allowed for measurement of monensin potentially reaching the shallow groundwater as a direct result of irrigation with lagoon water. Monensin was extracted from water samples via hydrophilic-lipophilic balance solid-phase extraction and quantified with liquid chromatography-mass spectrometry. Irrigation water was found to contain up to 1.6 μg L monensin, but monensin was only detected in monitoring wells surrounding the waste storage lagoon. Water chemistry changes in the wells bordering the irrigated field suggest that up to 7% of irrigation water reached groundwater within days of irrigation. The study suggests that contamination of groundwater with monensin can occur primarily by compromised waste storage systems and that rapid transport of monensin to groundwater is not likely to occur from a single irrigation event.
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