Chlorpyrifos fate in the Arctic: Importance of analyte structure in interactions with Arctic dissolved organic matter.

The insecticide and current use pesticide chlorpyrifos (CLP) is transported via global distillation to the Arctic where it may pose a threat to this ecosystem. CLP is readily detected in Arctic environmental compartments, but current research has not studied its partitioning between water and dissolved organic matter (DOM) nor the role of photochemistry in CLP's fate in aquatic systems. Here, the partition coefficients of CLP were quantified with various types of DOM isolated from the Arctic and an International Humic Substances Society (IHSS) reference material Suwannee River natural organic matter (SRNOM). While CLP readily partitions to DOM, CLP exhibits a significantly higher binding constant with Arctic lacustrine DOM relative to fluvial DOM or SRNOM. The experimental partitioning coefficients (KDOC) were compared to a calculated value estimated using poly parameter linear free energy relationship (pp-LFER) and was found to be in good agreement with SRNOM, but none of the Arctic DOMs. We found that Arctic KDOC values decrease with increasing SUVA254, but no correlations were observed for the other DOM compositional parameters. DOM also mediates the photodegradation of CLP, with stark differences in photo-kinetics using Arctic DOM isolated over time and space. This work highlights the chemo-diversity of Arctic DOM relative to IHSS reference materials and highlights the need for in-depth characterization of DOM that transcends the current paradigm based upon terrestrial and microbial precursors.

Small and large-scale distribution of four classes of antibiotics in sediment: association with metals and antibiotic resistance genes.

Antibiotic chemicals and antibiotic resistance genes enter the environment via wastewater effluents as well as from runoff from agricultural operations. The relative importance of these two sources, however, is largely unknown. The relationship between the concentrations of chemicals and genes requires exploration, for antibiotics in the environment may lead to development or retention of resistance genes by bacteria. The genes that confer resistance to metal toxicity may also be important in antibiotic resistance. In this work, concentrations of 19 antibiotics (using liquid chromatography tandem mass spectrometry), 14 metals (using inductively coupled plasma-mass spectrometry), and 45 metal, antibiotic, and antibiotic-resistance associated genes (using a multiplex, microfluidic quantitative polymerase chain reaction method) were measured in 13 sediment samples from two large rivers as well as along a spatial transect in a wastewater effluent-impacted lake. Nine of the antibiotics were detected in the rivers and 13 were detected in the lake. Sixteen different resistance genes were detected. The surrounding land use and proximity to wastewater treatment plants are important factors in the number and concentrations of antibiotics detected. Correlations among antibiotic chemical concentrations, metal concentrations, and resistance genes occur over short spatial scales in a lake but not over longer distances in major rivers. The observed correlations likely result from the chemicals and resistance genes arising from the same source, and differences in fate and transport over larger scales lead to loss of this relationship.

Sedimentary record of antibiotic accumulation in Minnesota Lakes.

The widespread detection of antibiotics in the environment is concerning because antibiotics are designed to be effective at small doses. The objective of this work was to quantify the accumulation rates of antibiotics used by humans and animals, spanning several major antibiotic classes (sulfonamides, tetracyclines, fluoroquinolones, and macrolides), in Minnesota lake-sediment cores. Our goal was to determine temporal trends, the major anthropogenic source to these lacustrine systems, and the importance of natural production. A historical record of usage trends for ten human and/or animal-use antibiotics (four sulfonamides, three fluoroquinolones, one macrolide, trimethoprim, and lincomycin) was faithfully captured in the sediment cores. Nine other antibiotics were not detected. Ofloxacin, trimethoprim, sulfapyridine, and sulfamethazine were detected in all of the anthropogenically-impacted studied lakes. Maximum sediment fluxes reached 20.5ngcm-2yr-1 (concentration 66.1ng/g) for ofloxacin, 1.2ngcm-2yr-1 (1.2ng/g) for trimethoprim, 3.3ngcm-2yr-1 (11.3ng/g) for sulfapyridine, and 1.0ngcm-2yr-1 (1.6ng/g) for sulfamethazine, respectively. Natural production of lincomycin may have occurred in one lake at fluxes ranging from 0.4 to 1.8ngcm-2yr-1 (0.1 to 5.8ng/g). Wastewater effluent appears to be the primary source of antibiotics in the studied lakes, with lesser inputs from agricultural activities.

Quantification of Hydroxylated Polybrominated Diphenyl Ethers (OH-BDEs), Triclosan, and Related Compounds in Freshwater and Coastal Systems.

Hydroxylated polybrominated diphenyl ethers (OH-BDEs) are a new class of contaminants of emerging concern, but the relative roles of natural and anthropogenic sources remain uncertain. Polybrominated diphenyl ethers (PBDEs) are used as brominated flame retardants, and they are a potential source of OH-BDEs via oxidative transformations. OH-BDEs are also natural products in marine systems. In this study, OH-BDEs were measured in water and sediment of freshwater and coastal systems along with the anthropogenic wastewater-marker compound triclosan and its photoproduct dioxin, 2,8-dichlorodibenzo-p-dioxin. The 6-OH-BDE 47 congener and its brominated dioxin (1,3,7-tribromodibenzo-p-dioxin) photoproduct were the only OH-BDE and brominated dioxin detected in surface sediments from San Francisco Bay, the anthropogenically impacted coastal site, where levels increased along a north-south gradient. Triclosan, 6-OH-BDE 47, 6-OH-BDE 90, 6-OH-BDE 99, and (only once) 6'-OH-BDE 100 were detected in two sediment cores from San Francisco Bay. The occurrence of 6-OH-BDE 47 and 1,3,7-tribromodibenzo-p-dioxin sediments in Point Reyes National Seashore, a marine system with limited anthropogenic impact, was generally lower than in San Francisco Bay surface sediments. OH-BDEs were not detected in freshwater lakes. The spatial and temporal trends of triclosan, 2,8-dichlorodibenzo-p-dioxin, OH-BDEs, and brominated dioxins observed in this study suggest that the dominant source of OH-BDEs in these systems is likely natural production, but their occurrence may be enhanced in San Francisco Bay by anthropogenic activities.