Plant Assimilation Kinetics and Metabolism of 2-Mercaptobenzothiazole Tire Rubber Vulcanizers by Arabidopsis.

2-Mercaptobenzothiazole (MBT) is a tire rubber vulcanizer found in potential sources of reclaimed water where it may come in contact with vegetation. In this work, we quantified the plant assimilation kinetics of MBT using Arabidopsis under hydroponic conditions. MBT depletion kinetics in the hydroponic medium with plants were second order (t1/2 = 0.52 to 2.4 h) and significantly greater than any abiotic losses (>18 times faster; p = 0.0056). MBT depletion rate was related to the initial exposure concentration with higher rates at greater concentrations from 1.6 µg/L to 147 µg/L until a potentially inhibitory level (1973 µg/L) lowered the assimilation rate. 9.8% of the initial MBT mass spike was present in the plants after 3 h and decreased through time. In-source LC-MS/MS fragmentation revealed that MBT was converted by Arabidopsis seedlings to multiple conjugated-MBT metabolites of differential polarity that accumulate in both the plant tissue and hydroponic medium; metabolite representation evolved temporally. Multiple novel MBT-derived plant metabolites were detected via LC-QTOF-MS analysis; proposed transformation products include glucose and amino acid conjugated MBT metabolites. Elucidating plant transformation products of trace organic contaminants has broad implications for water reuse because plant assimilation could be employed advantageously in engineered natural treatment systems, and plant metabolites in food crops could present an unintended exposure route to consumers.

Rapid Phytotransformation of Benzotriazole Generates Synthetic Tryptophan and Auxin Analogs in Arabidopsis.

Benzotriazoles (BTs) are xenobiotic contaminants widely distributed in aquatic environments and of emerging concern due to their polarity, recalcitrance, and common use. During some water reclamation activities, such as stormwater bioretention or crop irrigation with recycled water, BTs come in contact with vegetation, presenting a potential exposure route to consumers. We discovered that BT in hydroponic systems was rapidly (approximately 1-log per day) assimilated by Arabidopsis plants and metabolized to novel BT metabolites structurally resembling tryptophan and auxin plant hormones; <1% remained as parent compound. Using LC-QTOF-MS untargeted metabolomics, we identified two major types of BT transformation products: glycosylation and incorporation into the tryptophan biosynthetic pathway. BT amino acid metabolites are structurally analogous to tryptophan and the storage forms of auxin plant hormones. Critical intermediates were synthesized (authenticated by (1)H/(13)C NMR) for product verification. In a multiple-exposure temporal mass balance, three major metabolites accounted for >60% of BT. Glycosylated BT was excreted by the plants into the hydroponic medium, a phenomenon not observed previously. The observed amino acid metabolites are likely formed when tryptophan biosynthetic enzymes substitute synthetic BT for native indolic molecules, generating potential phytohormone mimics. These results suggest that BT metabolism by plants could mask the presence of BT contamination in the environment. Furthermore, BT-derived metabolites are structurally related to plant auxin hormones and should be evaluated for undesirable biological effects.

Uptake of contaminants of emerging concern by the bivalves Anodonta californiensis and Corbicula fluminea.

Uptake of seven contaminants regularly detected in surface waters and spanning a range of hydrophobicities (log D(ow) -1 to 5) was studied for two species of freshwater bivalves, the native mussel Anodonta californiensis and the invasive clam Corbicula fluminea. Batch systems were utilized to determine compound partitioning, and flow-through systems, comparable to environmental conditions in effluent dominated surface waters, were used to determine uptake and depuration kinetics. Uptake of compounds was independent of bivalve type. Log bioconcentration factor (BCF) values were correlated with log D(ow) for nonionized compounds with the highest BCF value obtained for triclocarban (TCC). TCC concentrations were reduced in the water column due to bivalve activity. Anionic compounds with low D(ow) values, i.e., clofibric acid and ibuprofen, were not removed from water, while the organic cation propranolol showed biouptake similar to that of TCC. Batch experiments supported compound uptake patterns observed in flow-through experiments. Contaminant removal from water was observed through accumulation in tissue or settling as excreted pseudofeces or feces. The outcomes of this study indicate the potential utility of bivalve augmentation to improve water quality by removing hydrophobic trace organic compounds found in natural systems.

Emissions of polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans during 2010 and 2011 in Zurich, Switzerland.

Persistent organic pollutants (POPs) are ubiquitous contaminants of environmental and human health relevance, but their emissions into the environment are still poorly known. In this study, concentrations of selected POPs were measured in ambient air in Zurich, Switzerland, and interpreted with a multimedia mass balance model. The aim of the combination of measurements and modeling was to back-calculate atmospheric emission rates of POPs. Measurements were performed in summer 2010 and winter 2011 and target analytes included polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Estimated emissions were higher in summer than in winter. Emission estimates for Zurich can be extrapolated to annual averages for Switzerland of 312 kg·a(-1) (39 mg·capita(-1)·a(-1)), 53 kg·a(-1) (7 mg·capita(-1)·a(-1)), and 3 kg·a(-1) (0.4 mg·capita(-1)·a(-1), 94 g WHO98-TEQ·a(-1), 65 g I-TEQ·a(-1)) for the six indicator PCBs (iPCBs), the twelve coplanar dioxin-like PCBs (dlPCBs), and the 17 2,3,7,8-chlorosubstituted PCDD/Fs, respectively. The emission rates of iPCBs are in agreement with existing emission inventories, whereas for PCDD/Fs the emissions are five times higher than the estimates from the Swiss national emission inventory. Emissions of dlPCBs in Switzerland are presented here for the first time. Our study also provides the first seasonally resolved emission rates of POPs, which were determined with our combined measurement and modeling approach. These findings highlight the relevance of ongoing sources of POPs, even decades after regulations aiming to reduce or eliminate sources were established.

Evaluation of a Five-Probe Metabolic Control Cocktail in Long-Term Cocultured Human Hepatocytes.

Hepatocyte cocultures like HepatoPac have become more frequently used for the assessment of the intrinsic clearance of slowly metabolised drugs during drug discovery due to a superiority in enzymatic activity over time compared to liver microsomal fractions and suspended primary hepatocytes. However, the relatively high cost and practical limitations prevent several quality control compounds to be included in studies and the activities of many important metabolic enzymes are consequently often not monitored. In this study, we have evaluated the possibility for a cocktail approach of quality control compounds in the human HepatoPac system to ensure adequate activity of the major metabolising enzymes. Five reference compounds were selected based on their known metabolic substrate profile in order to capture major CYP and non-CYP metabolic pathways in the incubation cocktail. The intrinsic clearance of the reference compounds when incubated as singlets or in a cocktail was compared and no considerable difference was observed. We show here that a cocktail approach of quality control compounds allows for easy and efficient evaluation of the metabolic competency of the hepatic coculture system over an extended incubation period.

Quantifying diffuse and point inputs of perfluoroalkyl acids in a nonindustrial river catchment.

Recently, the role of diffuse inputs of perfluoroalkyl acids (PFAAs) into surface waters has been investigated. It has been observed that river loads increased during rain and that street runoff contained considerable loads of PFAAs. This study aims at quantifying these diffuse inputs and identifying the initial sources in a small nonindustrial river catchment. The river was sampled in three distinct subcatchments (rural, urban, and wastewater treatment plant) at high temporal resolution during two rain events and samples were analyzed for perfluorocarboxylates and perfluorosulfonates. Additionally, rain, stormwater runoff, wastewater effluent, and drinking water were sampled. PFAA concentrations in river water were all low (e.g., < 10 ng/L for perfluorooctanoate, PFOA), but increased during rainfall. PFAA concentrations and water discharge data were integrated into a mass balance assessment that shows that 30-60% of PFAA loads can be attributed to diffuse inputs. Rain contributed 10-50% of the overall loads, mobilization of dry deposition and outdoor release of PFAA from products with 20-60%. We estimated that within a year 2.5-5 g of PFOA originating from rain and surface runoff are emitted into this small catchment (6 km(2), 12,500 persons).

Biomagnification of perfluorinated compounds in a remote terrestrial food chain: Lichen-Caribou-wolf.

The biomagnification behavior of perfluorinated carboxylates (PFCAs) and perfluorinated sulfonates (PFSAs) was studied in terrestrial food webs consisting of lichen and plants, caribou, and wolves from two remote northern areas in Canada. Six PFCAs with eight to thirteen carbons and perfluorooctane sulfonate (PFOS) were regularly detected in all species. Lowest concentrations were found for vegetation (0.02-0.26 ng/g wet weight (ww) sum (Σ) PFCAs and 0.002-0.038 ng/g ww PFOS). Wolf liver showed highest concentrations (10-18 ng/g ww ΣPFCAs and 1.4-1.7 ng/g ww PFOS) followed by caribou liver (6-10 ng/g ww ΣPFCAs and 0.7-2.2 ng/g ww PFOS). Biomagnification factors were highly tissue and substance specific. Therefore, individual whole body concentrations were calculated and used for biomagnification and trophic magnification assessment. Trophic magnification factors (TMF) were highest for PFCAs with nine to eleven carbons (TMF = 2.2-2.9) as well as PFOS (TMF = 2.3-2.6) and all but perfluorooctanoate were significantly biomagnified. The relationship of PFCA and PFSA TMFs with the chain length in the terrestrial food chain was similar to previous studies for Arctic marine mammal food web, but the absolute values of TMFs were around two times lower for this study than in the marine environment. This study demonstrates that challenges remain for applying the TMF approach to studies of biomagnification of PFCAs and PFSAs, especially for terrestrial animals.

Competing mechanisms for perfluoroalkyl acid accumulation in plants revealed using an Arabidopsis model system.

Perfluoroalkyl acids (PFAAs) bioaccumulate in plants, presenting a human exposure route if present in irrigation water. Curiously, accumulation of PFAAs in plant tissues is greatest for both the short-chain and long-chain PFAAs, generating a U-shaped relationship with chain length. In the present study, the authors decouple competing mechanisms of PFAA accumulation using a hydroponic model plant system (Arabidopsis thaliana) exposed to a suite of 10 PFAAs to determine uptake, depuration, and translocation kinetics. Rapid saturation of root concentrations occurred for all PFAAs except perfluorobutanoate, the least-sorptive (shortest-chain) PFAA. Shoot concentrations increased continuously, indicating that PFAAs are efficiently transported and accumulate in shoots. Tissue concentrations of PFAAs during depuration rapidly declined in roots but remained constant in shoots, demonstrating irreversibility of the translocation process. Root and shoot concentration factors followed the U-shaped trend with perfluoroalkyl chain length; however, when normalized to dead-tissue sorption, this relationship linearized. The authors therefore introduce a novel term, the "sorption normalized concentration factor," to describe PFAA accumulation in plants; because of their hydrophobicity, sorption is the determining factor for long-chain PFAAs, whereas the shortest-chain PFAAs are most effectively transported in the plant. The present study provides a mechanistic explanation for previously unexplained PFAA accumulation trends in plants and suggests that shorter-chained PFAAs may bioaccumulate more readily in edible portions.

Emissions of polybrominated diphenyl ethers (PBDEs) in Zurich, Switzerland, determined by a combination of measurements and modeling.

Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants but they are of concern and are currently being phased-out because of their environmentally hazardous properties and their potential to cause adverse health effects. We analyzed PBDEs in Zurich, Switzerland, and applied a multi-media environmental fate model to back-calculate the rate of PBDE emission to air. PBDE concentrations in ambient air were measured in summer 2010 and winter 2011 in the city center of Zurich. Concentrations were higher in summer (sum PBDEs 118-591 pg m(-3)) than in winter (sum PBDEs 17-151 pg m(-3)), and are on the upper end of concentrations reported in literature for urban sites with no point sources of PBDEs. The emissions derived from our measurements (summer: 53-165 µg capita(-1) d(-1), winter: 25-112 µg capita(-1) d(-1)) and extrapolated to annual emissions for Switzerland (114-406 kg a(-1)) lie in the middle of ranges reported on the basis of substance flow analyses and emission inventories. The difference between summer and winter emissions is small compared to the difference that would be expected from the temperature dependence of PBDE vapor pressure, which would be consistent with emissions occurring to a large extent from flame-proofed materials located indoors under nearly constant temperature conditions and/or emissions to air occurring by suspension of particles containing PBDEs. Compared to previous studies in Switzerland, concentrations and emissions of PBDEs appear to have increased during the last five years with an increasing contribution of decabromodiphenyl ether, despite the addition of PBDEs to national and international regulations.

Atmospheric fate of poly- and perfluorinated alkyl substances (PFASs): I. Day-night patterns of air concentrations in summer in Zurich, Switzerland.

Poly- and perfluorinated alkyl substances (PFASs) are anthropogenic pollutants ubiquitously found in the environment. Volatile PFASs are likely transported atmospherically over long ranges, but identification and quantification of emission sources is a challenging task. In this work, special meteorological conditions were utilized to quantify atmospheric emissions of Zurich City, Switzerland with a dual approach of modeling and field measurements. During high pressure systems in summer, a stable nocturnal boundary layer is formed in which pollutants are enriched. For volatile PFASs, a diel pattern of high concentrations in the night and low concentrations during the day was observed in Zurich, which is likely due to the atmospheric boundary layer dynamics. These results enable to model the emission source strength of Zurich City with a multimedia mass balance model in an accompanying paper. Cluster analyses suggested that perfluorocarboxylates (PFCAs) are a result of degradation of volatile precursors and direct emissions.

Atmospheric fate of poly- and perfluorinated alkyl substances (PFASs): II. Emission source strength in summer in Zurich, Switzerland.

Fluorotelomer alcohols (FTOHs) and perfluorooctane sulfonamides (FOSAs) are present in consumer products and are semi-volatile precursors of persistent perfluoroalkyl acids (PFAAs). The high variability of levels of FTOHs and FOSAs in products makes it difficult to derive FTOH- and FOSA-emissions from urban areas based on emission factors. Here we used a multimedia mass balance model that describes the day-night cycle of semi-volatile organic chemicals in air to interpret measurements of 8:2 FTOH, 10:2 FTOH, MeFOSA and EtFOSA from a sampling campaign in summer 2010 in Zurich, Switzerland. The estimated emission source strength of the four substances follows the sequence: 8:2 FTOH (2.6 g/h) > 10:2 FTOH (0.75 g/h) > MeFOSA (0.08 g/h) > EtFOSA (0.05 g/h). There is no FTOHs- or FOSAs-related industry in Zurich. Accordingly, our estimates are representative of diffusive emissions during use and disposal of consumer products, and describe noticeable sources of these PFASs to the environment.

Identification of perfluoroalkyl acid sources in Swiss surface waters with the help of the artificial sweetener acesulfame.

Anthropogenic perfluorinated compounds (PFCs), especially the perfluoroalkyl acids (PFAAs) are ubiquitously found in surface waters around the globe. Emissions from households, industries and also atmospheric transport/deposition are discussed as the possible sources. In this study, these sources are evaluated using Switzerland as the study area. Forty-four surface water locations in different rivers and an Alpine lake were investigated for 14 PFAAs, four precursors and acesulfame, an artificial sweetener used as a population marker. Concentrations of individual PFAAs were generally low, between 0.02 and 10 ng/L. Correlation analysis showed that some PFAAs concentrations correlated well with population and less with catchment area, indicating that emissions from population, i.e., from consumer products, is the most important source to surface waters in Switzerland. The correlation with the population marker acesulfame confirmed this observation but highlighted also a few elevated PFAA levels, some of which could be attributed to industrial emissions.

Comparison of two extraction methods for the analysis of per- and polyfluorinated chemicals in digested sewage sludge.

A rapid and reliable analytical method, based on ion-pair extraction, clean-up on Envicarb cartridge and detection by liquid chromatography-tandem mass spectrometry (LC-MS/MS), was developed for determination of 17 per- and polyfluorinated chemicals (PFCs) in digested sewage sludge. Envicarb cartridge and six labeled internal standards were selected for the elimination/reduction and correction of matrix effects, respectively. As a result, the matrix effect for perfluorooctane sulfonamides (FOSAs) and perfluorocarboxylic acids (PFCAs) with carbon chain length from C6 to C14 was lowered to a range of -14% to +28%. However, the matrix effect for other analytes was still great mainly due to the absence of appropriate internal standard. Mean recoveries of the target analytes based on matrix spikes, at different spike levels (10-300ng/g), ranged from 70% to 169%. Relative standard deviations (RSDs) were in the range of 2-20% at different spike levels. The limit of quantification (LOQ) ranged between 0.6 and 30ng/g. The method was successfully applied to several sewage sludge samples from wastewater treatment plants nearby Zürich, Switzerland. In addition, by comparing the accuracy and precision of ion-pair extraction method and methanol extraction method, we further demonstrated that the ion-pair extraction method can be used for the analysis of PFCs in sludge samples. To our knowledge, this is the first study to extract the PFCs in sewage sludge with ion-pair method and to find unsaturated fluorotelomer carboxylic acids (FTUCAs) in sewage sludge.

Historical profiles of chlorinated paraffins and polychlorinated biphenyls in a dated sediment core from Lake Thun (Switzerland).

A dated sediment core from Lake Thun covering the last 120 years was analyzed to get an overview of the historical trend of the chlorinated paraffin (CP) and polychlorinated biphenyl (PCB) deposition, because CPs and PCBs have/had similar applications as plasticizers and flame retardants. Total CP concentrations (sum of short chain (SCCP), medium chain (MCCP), and long chain CPs (LCCP)) showed a steep increase in the 1980s and a more-or-less stable level of 50 ng g(-1) dry weight (dw) since then. The concentration-time profile is in good agreement with the available information on global production data. The quantification of higher chlorinated SCCPs using electron capture negative ionization low resolution mass spectrometry (ECNI-LRMS) revealed an increase in recent years. In addition, the degree of chlorination of SCCPs has strongly increased during the past 40 years, which may indicate its use as an additive for plastics, paints, and coatings. Furthermore, PCBs were analyzed in dated sediment slices. The PCB concentrations (sum of the six indicator congeners) peaked around 1969 (18 ng g(-1) dw) and decreased to 1.3 ng g(-1) dw in the surface layer corresponding to 2004. The peak level of CPs exceeded those of PCBs by about a factor of 3.

Sediment record and atmospheric deposition of brominated flame retardants and organochlorine compounds in Lake Thun, Switzerland: lessons from the past and evaluation of the present.

Chronology of brominated fame retardants (BFRs), a class of currentlywidely used chemicals, was compared to the respective historical profiles of legacy organochlorine compounds in three dated sediment cores from a prealpine lake (Lake Thun, Switzerland). Concentrations of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) started to increase in the 1980s-1990s. In the more recent sediment layers, PBDEs still had steady or increasing concentrations, whereas for HBCDs one sediment core revealed a decreasing trend. In contrast to the contemporary BFRs, concentrations of legacy organochlorines, such as polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and dichlorodiphenyl trichloroethane (DDT), peaked in deeper sediment layers deposited some decades ago. Measurements of atmospheric deposition and evaluation of wastewater discharges pointtoward deposition on the lake surface as a relevant input pathway and wastewater as a minor source of POPs in Lake Thun. The effect of the environmental awareness and the regulations taken in the 1970s to reduce environmental pollution of organochlorines is well reflected in the analyzed sediment cores. The sediment burden closely follows estimated time trends of consumption and emission of PCBs and DDT. The current residues in sediment of BFRs are still lower than the historical peak levels of organochlorines. However, current atmospheric deposition of BFRs is similar to deposition of PCBs. Considering the high amount of BFRs presently stocked in the anthroposphere in flame proofed materials, further measures to reduce emissions during BFRs life cycle are recommended to prevent high environmental pollution as it occurred for the organochlorine compounds.