Claire Alary

Thickness and material selection of polymeric passive samplers for polycyclic aromatic hydrocarbons in water: Which more strongly affects sampler properties?

Three configurations of single-phase polymer passive samplers made of polyoxymethylene (POM), silicone rubber, and polyethylene (PE) were simultaneously calibrated in laboratory experiments by determining their partitioning coefficients and the POM diffusion coefficients and by validating a kinetic accumulation model. In addition, the performance of each device was evaluated under field conditions. With the support of the developed model, the device properties are discussed with regard to material selection and polymer thickness. The results show that a samplers properties, such as its concentration-averaging period and ability to sample a large amount of polycyclic aromatic hydrocarbons, are widely affected by material selection. Sampler thickness also allows modulation of the properties of the device but with a much lower magnitude. Selection of the appropriate polymer and/or thickness allows samplers to be adapted either for quick equilibration or for the kinetic accumulation regime and promotes either membrane or water boundary layer control of the kinetic accumulation. In addition, membrane-controlled or equilibrated compounds are quantified with greater accuracy because they are not corrected by the performance reference compounds approach. However, the averaged concentrations cannot be assessed when compounds reach equilibrium in the sampler, whereas membrane-controlled devices remaining in the kinetic accumulation regime provide averaged concentrations without requiring performance reference compound correction; detection limits are then increased because of the higher mass transfer resistance of the membrane. Environ Toxicol Chem 2016;35:1708-1717.

Calibration and response of an agarose gel based passive sampler to record short pulses of aquatic organic pollutants

A passive sampler inspired from previous devices was developed for the integrative sampling of a broad range of contaminants in the water column. Our primary objective was to improve the performance of the device to provide accurate and averaged pollutant water concentrations. For this purpose, an agarose diffusive gel was used as the boundary layer that drives the analyte uptake rate. Contrary to conventional passive samplers, the developed device does not require the sampling rates to be corrected for exposure conditions (e.g. hydrodynamic flow) because the diffusive gel boundary layer selected was sufficiently large to control the pollutant diffusion rate from the aqueous phase. The compounds diffusion coefficients in agarose gel and the gel thickness are the only required data to accurately calculate the time weighted averaged water concentration of pollutants. The performance of the developed sampler was evaluated in the laboratory under two contamination scenarios and in the field in 8 contrasting exposure sites for a selection of 16 emerging pollutants and pesticides. The results show that detection limits of this method are environmentally relevant and allow the determination of the averaged pollutant concentrations. Additionally, the ability of the device to sense very short contamination pulses (5-320min) was evaluated through a theoretical approach and laboratory tests. Results show that the device is suitable for sampling contamination pulses as short as 5min without deviation from the actual average concentrations of pollutants.

A new application of passive samplers as indicators of in-situ biodegradation processes

In this paper, a method for evaluating the in-situ degradation of nitro polycyclic aromatic hydrocarbons (nitro-PAH) in sediments is presented. The methodology is adapted from the passive sampler technique, which commonly uses the dissipation rate of labeled compounds loaded in passive sampler devices to sense the environmental conditions of exposure. In the present study, polymeric passive samplers (made of polyethylene strips) loaded with a set of labeled polycyclic aromatic hydrocarbons (PAH) and nitro-PAH were immersed in sediments (in field and laboratory conditions) to track the degradation processes. This approach is theoretically based on the fact that a degradation process induces a steeper concentration gradient of the labeled compounds in the surrounding sediment, thereby increasing their compound dissipation rates compared with their dissipation in abiotic conditions. Postulating that the degradation magnitude is the same for the labeled compounds loaded in polyethylene strips and for their native homologs that are potentially present in the sediment, the field degradation of 3 nitro-PAH (2-nitro-fluorene, 1-nitro-pyrene, 6-nitro-chrysene) was semi-quantitatively analyzed using the developed method.

Assessing the transport of PAH in the surficial sediment layer by passive sampler approach

A new method based on passive samplers has been developed to assess the diffusive flux of fluorene, fluoranthene and pyrene in the sediment bed and across the sediment-water interface. The dissolved compound concentration gradient in the sediment in the vertical direction was measured at the outlet of a storm water pond by using polyethylene strips as passive samplers. Simultaneously, the dissipation of a set of tracer compounds preloaded in the passive samplers was measured to estimate the effective diffusion coefficients of the pollutants in the sediment. Both measurements were used to evaluate the diffusive flux of the compounds according to Ficks first law. The diffusive fluxes of the 3 studied compounds have been estimated with a centimetre-scale resolution in the upper 44cm of the sediment. According to the higher compound diffusion coefficient and the steeper concentration gradient in the surficial sediment layer, the results show that the net flux of compounds near the sediment interface (1cm depth) is on average 500 times higher than in the deep sediment, with average fluxes at 1cm depth on the order of 5, 0.1 and 0.1ng/m2/y for fluorene, fluoranthene and pyrene, respectively.