Measuring nonpolar organic contaminant partitioning in three Norwegian sediments using polyethylene passive samplers.
ABSTRACT Freely dissolved pore water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), penta- and hexachlorobenzene (PeCB and HCB), octachlorostyrene (OCS), p,p'-DDE and p,p'-DDD were measured in bottom sediments from three sites in Norway. Sediments were from Aker Brygge, site of a former shipyard in the inner part of Oslofjord, Frierfjord in the Grenlandsfjord area, impacted during the 50 year-long activity of a magnesium smelter plant, and from Kristiansand harbour, site with high industrial activity. Low density polyethylene (LDPE) membrane samplers were exposed to these sediments in laboratory incubation under constant and low-level agitation for periods of 1, 2, 6, 13, 23 and 50 days. Freely dissolved pore water concentrations were estimated from contaminant masses accumulated and sampling rates obtained from the measurement of kinetics of dissipation of performance reference compounds (PRCs). Marked differences in freely dissolved PAH concentrations and resulting organic carbon-normalised sediment-pore water partition coefficients, logK(TOC), between these three sediments could be observed despite the generally similar total sediment concentrations. In contrast with the PAH data, partitioning of PCBs and other organochlorine compounds (OCs) was relatively similar in all three sediments. For sediments from Frierfjord and Kristiansand, logK(TOC) values were lower for PCBs/OCs than for PAHs, indicating higher availability. Similar partitioning of PAHs and PCBs/OCs was found for sediments from Aker Brygge. No simple logK(oc)-logK(ow) relationships could model these data successfully. These results support the notion that the assessment of the risk posed by these compounds present in sediments in most cases requires actual measurement of contaminant availability.
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ABSTRACT: Pore concentration and partition coefficients of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in sediments from five distinct contaminated sites in France (marine harbour, rivers canals and highway sedimentation tank). The assessment of the risk caused by such micropollutants requires, in most cases, the measurement of their availability. To assess this availability, low density polyethylene (LDPE) membrane samplers were exposed to these sediments under constant and low-level agitation over a period of 46days. Freely dissolved pore water contaminant concentrations were estimated from the concentration at equilibrium in the LDPE membrane. The depletion of contaminants in the sediments was monitored by the use of performance reference compounds (PRCs). Marked differences in freely dissolved PAH and PCB concentrations and resulting sediment-pore water partition coefficients between these five sediments were observed. Data set was tested onto different empirical and mechanistic models. As final findings, triple domain sorption (a total organic carbon, black carbon and oil phase model) could model PCB data successfully whereas the best fitting for PAH partitioning was obtained by Raoult's Law model.Science of The Total Environment 12/2013; · 3.26 Impact Factor
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ABSTRACT: Passive sampling methods (PSMs) allow the quantification of the freely dissolved concentration (Cfree ) of an organic contaminant even in complex matrices such as sediments. Cfree is directly related to a contaminant's chemical activity, which drives spontaneous processes including diffusive uptake into benthic organisms and exchange with the overlying water column. Consequently, Cfree provides a more relevant dose metric than total sediment concentration. Recent developments in PSMs have significantly improved our ability to reliably measure even very low levels of Cfree . Application of PSMs in sediments is preferably conducted in the equilibrium regime, where freely dissolved concentrations in the sediment are well linked to the measured concentration in the sampler via analyte-specific partition ratios. The equilibrium condition can then be assured by measuring a time series or a single time point using passive samplers with different surface to volume ratios. Sampling in the kinetic regime is also possible and generally involves the application of performance references compounds for the calibration. Based on previous research on hydrophobic organic contaminants, it is concluded that Cfree allows a direct assessment of (1) contaminant exchange and equilibrium status between sediment and overlying water, (2) benthic bioaccumulation and (3) potential toxicity to benthic organisms. Thus, the use of PSMs to measure Cfree provides an improved basis for the mechanistic understanding of fate and transport processes in sediments and has the potential to significantly improve risk assessment and management of contaminated sediments. Integr Environ Assess Manag © 2013 SETAC.Integrated Environmental Assessment and Management 02/2014; 10(2):197-209.
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ABSTRACT: Passive sampling represents a cost-effective approach and is more representative than grab sampling for the determination of contaminant concentrations in freshwaters. In this study, we performed the calibration of a promising tool, the passive Stir Bar Sorptive Extraction (SBSE), which has previously shown good performances for semi-quantitative monitoring of pesticides in a field study. We determined the sampling rates and lag-phases of 18 moderately hydrophobic to hydrophobic agricultural pesticides (2.18 < log Kow < 5.11) from different chemical classes including triazines, substituted ureas, triazoles and organophosphate compounds. We also realised an elimination experiment to identify a performance reference compound (PRC). A flow-through calibration experiment was realised for 7 days at constant concentrations of target pesticides in tap water, under controlled temperature (20 °C) and flow velocity (2.5 cm s−1). Sampling rates were between 1.3 and 121 mL d−1 with satisfactory RSD for most pesticides (9-47%), and poor repeatability for 3 hydrophobic pesticides (59-83%). Lag-phases for all target pesticides were shorter than 2 h, demonstrating the efficiency of passive SBSE for the integration of transient concentration peaks of these contaminants in surface waters. The role of flow velocity on pesticide uptakes was investigated and we assumed a water boundary layer-controlled mass transfer for 5 pesticides with log Kow > 3.3. Among these pesticides, we selected fenitrothion to evaluate its elimination, along with its deuterated analogue. Results showed 82% elimination of both compounds over the 7-day experiment and isotropic exchange for fenitrothion, making fenitrothion-d6 a promising PRC candidate for in situ applicationsJournal of Chromatography A 01/2014; · 4.61 Impact Factor