Trends in monitoring pharmaceuticals and personal-care products in the aquatic environment by use of passive sampling devices.
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Biomedical subjects
Publications and source records attributed to Branislav Vrana.
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Passive sampling of dissolved pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low density polyethylene membrane, was developed and calibrated for the measurement of time weighted average (TWA) concentrations of hydrophobic pollutants in water. In this study, the exchange kinetics were modelled to obtain a better understanding of the mechanism of the accumulation process and to enable the measurement of TWA concentrations of hydrophobic pollutants in the field. An empirical relationship that enables the calculation of in situ sampling rates of chemicals using performance reference compounds was derived and its application was demonstrated in a field study in which TWA aqueous concentrations estimated from sampler data for target analytes were compared with TWA concentrations obtained from spot samples of water collected regularly during the sampler deployment period.
Solid phase microextraction (SPME) fibres coated with Carbowax/divinylbenzene and semi-permeable membrane devices (SPMDs) of standard configuration were used to obtain time-weighted average (TWA) field air concentrations of selected chlorinated semi-volatile compounds on a landfill, where large amounts of lindane by-products were deposited, together with other hazardous chemical residues in the past. Additionally, spot sampling with SPME fibres was performed to identify the emission hotspot and sampling rates were determined/predicted for the substances of interest. Both samplers yield comparable TWA air concentrations of lindane and its isomers and of DDT with its metabolites and gain in certainty about the landfill as remaining source of air pollution with these compounds in the region. Both SPME fibres and SPMDs (respective their modifications) can be recommended as sampling tools in process studies and larger air monitoring programmes. However, further calibration studies and field tests are necessary to obtain reliable sampling rates for a wider range of semi-volatile compounds.
Membrane-enclosed sorptive coating (MESCO) is a miniaturised monitoring device that enables integrative passive sampling of persistent, hydrophobic organic pollutants in water. The system combines the passive sampling with solventless preconcentration of organic pollutants from water and subsequent desorption of analytes on-line into a chromatographic system. Exchange kinetics of chemicals between water and MESCO was studied at different flow rates of water, in order to characterize the effect of variable environmental conditions on the sampler performance, and to identify a method for in situ correction of the laboratory-derived calibration data. It was found that the desorption of chemicals from MESCO into water is isotropic to the absorption of the analytes onto the sampler under the same exposure conditions. This allows for the in situ calibration of the uptake of pollutants using elimination kinetics of performance reference compounds and more accurate estimates of target analyte concentrations. A field study was conducted to test the sampler performance alongside spot sampling. A good agreement of contaminant patterns and water concentrations was obtained by the two sampling techniques.
An integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler-water partition coefficients did not significantly change with temperature.
The performance of an integrative passive sampler that consists of a C18 Empore disk sorbent receiving phase fitted with low density polyethylene membrane was optimised for the measurement of time-weighted average concentrations of hydrophobic micropollutants in water. A substantial improvement of sampling characteristics including the rate of sampling and the sampling precision was achieved by decreasing the internal sampler resistance to mass transfer of hydrophobic organic chemicals. This was achieved by adding a small volume of n-octanol, a solvent with high permeability (solubility [times] diffusivity) for target analytes, to the interstial space between the receiving sorbent phase and the polyethylene diffusion-limiting membrane.
Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.
The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.
The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but the potential effects of environmental variables affecting the accumulation of contaminants into SPMDs had not been characterized sufficiently, yet. To characterize the effect of hydrodynamic conditions on the contaminant uptake kinetics, accumulation of pentachlorobenzene, hexachlorobenzene, and hexachlorocyclohexane isomers from water into SPMD was studied at various water flow rates. The accumulation kinetics of hydrophobic compounds (log Kow > 4) are governed by the aqueous boundary layer in linear flow velocity range from 0.06 to 0.28 cm s(-1) and sensitive to slight changes in flow rate. The effect of flow velocity on the exchange kinetics increases with increasing hydrophobicity. Under faster, but still laminar flow conditions (0.28-1.14 cm s(-1)), the sensitivity to changes in flow decreases to a nonsignificant level for the substances under consideration. The results of this study confirm that the use of the laboratory-derived calibration data for estimation of analyte concentrations in the ambient environment is limited unless flow-sensitive performance reference compounds are used.