Stepping-up accurate quantification of chlorinated paraffins: Successful certification of the first matrix reference material.

BACKGROUND: Chlorinated paraffins (CPs) are industrial chemicals categorised as persistent organic pollutants because of their toxicity, persistency and tendency to long-range transport, bioaccumulation and biomagnification. Despite having been the subject of environmental attention for decades, analytical methods for CPs still struggle reaching a sufficient degree of accuracy. Among the issues negatively impacting the quantification of CPs, the unavailability of well-characterised standards, both as pure substances and as matrix (certified) reference materials (CRMs), has played a major role. The focus of this study was to provide a matrix CRM as quality control tool to improve the comparability of CPs measurement results. RESULTS: We present the process of certification of ERM®-CE100, the first fish reference material assigned with certified values for the mass fraction of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively). The certification was performed in accordance with ISO 17034:2016 and ISO Guide 35:2017, with the value assignment step carried out via an intercomparison of laboratories of demonstrated competence in CPs analysis and applying procedures based on different analytical principles. After confirmation of the homogeneity and stability of the CRM, two certified values were assigned for SCCPs, depending on the calibrants used: 31 ± 9 µg kg-1 and 23 ± 7 µg kg-1. The MCCPs certified value was established as 44 ± 17 µg kg-1. All assigned values are relative to wet weight in the CRM that was produced as a fish paste to enhance similarity to routine biota samples. SIGNIFICANCE AND NOVELTY: The fish tissue ERM-CE100 is the first matrix CRM commercially available for the analysis of CPs, enabling analytical laboratories to improve the accuracy and the metrological traceability of their measurements. The certified CPs values are based on results obtained by both gas and liquid chromatography coupled with various mass spectrometric techniques, offering thus a broad validity to laboratories employing different analytical methods and equipment.

Measurable Levels of Short-Chain Chlorinated Paraffins in Western Hudson Bay Fishes but Limited Biomagnification from Fish to Ringed Seals.

We investigated short-chain (C10-13 ) chlorinated paraffins (SCCP) in an Arctic marine food web. In zooplankton, fishes, and ringed seals from western Hudson Bay, Canada, SCCP concentrations ranged from 38.3 to 687 ng g-1 lipid weight. Monte Carlo-simulated trophic-adjusted biomagnification factors of individual SCCP congeners ranged from 0.07 to 0.55 for small pelagic fishes to seals. Despite relatively high concentrations in fishes, biomagnification of SCCPs within this food web appears limited. Environ Toxicol Chem 2021;40:2990-2999. © 2021 SETAC.

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil, influent, effluent, receiving water, and sediment of wastewater treatment plants in Canada.

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography - mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282-6.69µgL(-1), 7.75-135µgL(-1), and 1.53-26.9µgL(-1), respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009-0.045µgL(-1), <0.027-1.56µgL(-1), and <0.022-0.093µgL(-1), respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009-0.023µgL(-1), <0.027-1.48µgL(-1), and <0.022-0.151µgL(-1) for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003-0.049µgg(-1)dw, 0.011-5.84µgg(-1)dw, and 0.004-0.371µgg(-1)dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008-0.017µgg(-1)dw, <0.007-0.221µgg(-1)dw, and <0.009-0.711µgg(-1)dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.

Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection-gas chromatography-mass spectrometry.

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid-solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI-GC-MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS's associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4°C were stable within 29d; however, significant depletion of D6 (60-70%) occurred only after 3d. Whereas cVMS in sewage influent and effluent were stable at 4°C within 21d. cVMS in sediment sealed in amber glass jars at -20°C and in pentane extracts in vials at -15°C were stable during 1month under both storage conditions.

Bioremediation of tetrachloroethylene-contaminated groundwater in a model aquifer: effects on green frogs (Rana clamitans) and Xenopus laevis as potential wetland receptors.

Recent regulations require that the ecological effects of microorganisms introduced into the environment, such as for groundwater bioremediation, be assessed prior to their utilization. A native anuran (Rana clamitans) and a model anuran (Xenopus laevis) were used as potential wetland receptors of tetrachloroethylene (PCE)-contaminated groundwater, undergoing three bioremediation treatments: natural attenuation (NA), biostimulation (ST), and bioaugmentation (AU). Eggs of both species were exposed acutely (96 h) to remediated effluents. Xenopus tadpoles were chronically exposed to the effluents for 100 days and were screened for the presence of bacterial pathogens. There was no impact on the survivorship of the frogs exposed either acutely or chronically to the NA, ST, or AU effluents; nor was there any evidence of bacterial infection found, with the exception of control individuals. The results of these exposures suggest that bioremediation with KB-1trade mark culture poses a minimal threat to anuran development and survivorship.