Estimation of Measurement Uncertainties for the DGT Passive Sampler Used for Determination of Copper in Water.

Diffusion-based passive samplers are increasingly used for water quality monitoring. While the overall method robustness and reproducibility for passive samplers in water are widely reported, there has been a lack of a detailed description of uncertainty sources. In this paper an uncertainty budget for the determination of fully labile Cu in water using a DGT passive sampler is presented. Uncertainty from the estimation of effective cross-sectional diffusion area and the instrumental determination of accumulated mass of analyte are the most significant sources of uncertainty, while uncertainties from contamination and the estimation of diffusion coefficient are negligible. The results presented highlight issues with passive samplers which are important to address if overall method uncertainty is to be reduced and effective strategies to reduce overall method uncertainty are presented.

Evaluation of a passive sampler for the speciation of metals in urban runoff water.

Metals in urban runoff water need to be monitored in order to estimate fluxes and assess their impact on the aquatic environment. Passive sampling is a useful and reliable emerging tool for measuring time averaged concentrations of metals in water bodies. This paper describes the deployment of a passive sampler to measure Cu, Ni and Zn in an urban runoff water treatment facility. The concentrations derived from the passive samplers are compared to concentrations obtained from an automated water sampler which provides pooled spot water samples and to model predictions from the visualMINTEQ computer speciation code. Results show that visualMINTEQ predictions partly describe the metal speciation in non-equilibrium systems. In addition we conclude that passive samplers are useful for monitoring and characterization of metal speciation under chemodynamic conditions.

Performance of a passive sampler for the determination of time averaged concentrations of nitrate and phosphate in water.

A passive sampler device for the kinetic accumulation of nitrate (NO3(-)) and phosphate (HPO4(2-)) in water was developed and calibrated. The sampler incorporates an ion-exchange disk as the receiving phase and selectively collects nitrate and phosphate at sampling rates of 197 ± 43 and 75 ± 12 mL per day, respectively. Minimum exposure times under nutrient rich and nutrient poor conditions were estimated to be 3 and 27 days respectively for phosphate and 1 and 7 days respectively for nitrate. The influence of the environmental variables pH (5-9), temperature (7-21 °C) and turbulence (50-400 rpm) on sampling rates was investigated. Temperature was found to have a significant influence on uptake rates for both anions, while pH influenced phosphate only. Water turbulence did not influence the uptake rates under the studied conditions. A series of field studies was conducted at a municipal wastewater treatment plant. Results for the passive sampler were lower than concentrations obtained using conventional measurement methods, due to methodological differences, and biofouling was found to affect the results for sampling periods over 3 days. This study shows that passive sampling can be used to monitor nitrate and phosphate concentrations in aqueous media. The approach provides an interesting alternative to grab sampling as it yields time-averaged concentrations of the analytes.

Chemcatcher and DGT passive sampling devices for regulatory monitoring of trace metals in surface water.

This work aimed to evaluate whether the performance of passive sampling devices in measuring time-weighted average (TWA) concentrations supports their application in regulatory monitoring of trace metals in surface waters, such as for the European Union's Water Framework Directive (WFD). The ability of the Chemcatcher and the diffusive gradient in thin film (DGT) device sampler to provide comparable TWA concentrations of Cd, Cu, Ni, Pb and Zn was tested through consecutive and overlapping deployments (7-28 days) in the River Meuse (The Netherlands). In order to evaluate the consistency of these TWA labile metal concentrations, these were assessed against total and filtered concentrations measured at relatively high frequencies by two teams using standard monitoring procedures, and metal species predicted by equilibrium speciation modeling using Visual MINTEQ. For Cd and Zn, the concentrations obtained with filtered water samples and the passive sampling devices were generally similar. The samplers consistently underestimated filtered concentrations of Cu and Ni, in agreement with their respective predicted speciation. For Pb, a small labile fraction was mainly responsible for low sampler accumulation and hence high measurement uncertainty. While only the high frequency of spot sampling procedures enabled the observation of higher Cd concentrations during the first 14 days, consecutive DGT deployments were able to detect it and provide a reasonable estimate of ambient concentrations. The range of concentrations measured by spot and passive sampling, for exposures up to 28 days, demonstrated that both modes of monitoring were equally reliable. Passive sampling provides information that cannot be obtained by a realistic spot sampling frequency and this may impact on the ability to detect trends and assess monitoring data against environmental quality standards when concentrations fluctuate.

Evaluation of the Chemcatcher and DGT passive samplers for monitoring metals with highly fluctuating water concentrations.

Passive sampling devices accumulate chemicals continuously from water and can provide time weighted average (TWA) concentrations of pollutants over the exposure period. Hence, they offer a number of advantages over other conventional monitoring techniques such as spot or grab sampling. The diffusive gradient in thin film (DGT) and the Chemcatcher passive samplers can be used to provide TWA concentrations of labile metals, but the approaches to their calibration differ. DGT uses diffusion coefficients of metals in the hydrogel layer, whereas Chemcatcher uses metal specific uptake rates, with both sets of values obtained under controlled laboratory conditions with constant aqueous metal concentrations. However, little is known of how such samplers respond to fluctuating concentrations. We evaluated the responsiveness of these two passive sampling devices to rapidly changing concentrations of Cd, Cu, Ni, Pb and Zn in natural freshwater, over a relatively short deployment time. Maximum metal concentrations in water were varied between 70 and 140 microg L(-1). Experiments were carried out in a tank with a rotating carousel system and filled with Meuse river water, allowing a degree of control over experimental conditions while using natural river water. Fluctuating concentrations were obtained by stepwise addition of standard solutions of the metals. The reliability and accuracy of the TWA concentrations measured by the samplers were assessed by comparison with concentrations of the metals in spot samples of water taken regularly over the deployment period. The spot samples of water were either unfiltered (total), filtered (0.45 microm) or ultrafiltered (5 kDa). Predictive speciation modelling using the visual MINTEQ programme was also undertaken. There was reasonable agreement between the TWA concentrations of Cd and Ni obtained with Chemcatcher and DGT and the total Cd and Ni concentrations measured in repeated unfiltered spot samples. For elements (i.e. Cu, Pb, Zn) that associate to a significant degree with suspended solids, colloids or dissolved organic carbon, or form complexes with large organic ligands, optimum agreement was with the filtered or ultrafiltered fractions and with the predicted inorganic and inorganic-fulvic acid associated fractions. While Chemcatcher-based TWA concentration ranges for Cu and Zn were in best agreement with the total filtered fraction, there was lack of agreement for Pb. The combined use of DGT devices with open pore (OP) and restricted pore (RP) gels allowed the labile fraction of metal associated with large organic ligands or DOC to be differentiated and quantified, since this is available to DGT OP but unable to diffuse into the DGT RP. This evaluation of the two sampling devices clearly demonstrated their ability to react reliably to transient peaks in concentration of metal pollutants in water and indicated where future efforts are needed to improve calibration data. Such samplers may prove valuable in responding to the monitoring requirements of the European Union's Water Framework Directive.

Performance optimisation of a passive sampler for monitoring hydrophobic organic pollutants in water.

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.