Widespread use of organic chemicals in household and personal care products (HPCPs) and their discharge into aquatic systems means reliable, robust techniques to monitor environmental concentrations are needed. The passive sampling approach of diffusive gradients in thin-films (DGT) is developed here and demonstrated to provide in situ quantitative and time-weighted average (TWA) measurement of these chemicals in waters. The novel technique is developed for HPCPs, including preservatives, antioxidants and disinfectants, by evaluating the performance of different binding agents. Ultrasonic extraction of binding gels in acetonitrile gave good and consistent recoveries for all test chemicals. Uptake by DGT with HLB (hydrophilic-lipophilic-balanced) as the binding agent was relatively independent of pH (3.5-9.5), ionic strength (0.001-0.1 M) and dissolved organic matter (0-20 mg L), making it suitable for applications across a wide range of environments. Deployment time and diffusion layer thickness dependence experiments confirmed DGT accumulated chemicals masses are consistent with theoretical predictions. The technique was further tested and applied in the influent and effluent of a wastewater treatment plant. Results were compared with conventional grab-sampling and 24-h-composited samples from autosamplers. DGT provided TWA concentrations over up to 18 days deployment, with minimal effects from biofouling or the diffusive boundary layer. The field application demonstrated advantages of the DGT technique: it gives in situ analyte preconcentration in a simple matrix, with more quantitative measurement of the HPCP analytes.

It is essential to monitor pesticides in the environment to help ensure water and soil quality. The diffusive gradients in thin-films (DGT) technique can measure quantitative in situ labile (available) concentrations of chemicals in water, soil, and sediments. This study describes the systematic development of the DGT technique for nine current pesticides, selected to be representative of different classes with a wide range of properties, with two types of resins (HLB (hydrophilic-lipophilicbalanced) and XAD 18) as binding layer materials. The masses of pesticides accumulated by DGT devices were proportional to the deployment time and in inverse proportion to the thickness of the diffusive layer, in line with DGT theoretical predictions. DGT with both resin gels were tested in the laboratory for the effects of typical environmental factors on the DGT measurements. DGT performance was independent of the following: pH in the range of 4.7−8.2; dissolved organic matter concentrations <20 mg L −1 ; and ionic strength from 0.01 to 0.25 M, although it was slightly affected at 0.5 M in some cases. This confirms DGT as a sampler suitable for controlled studies of environmental processes affecting pesticides. Field applications of DGT to measure pesticides in situ in waters and controlled laboratory measurements on five different soils (prepared at fixed soil/water ratios) demonstrated DGT is a suitable tool for environmental monitoring in waters and for investigating chemical processes in soils.

The diffusive gradients in thin films (DGT) technique has been successfully and widely applied to investigate the labile fractions of inorganic contaminants in soils and sediments, but there have been almost no applications to organic contaminants. Here we developed and tested the approach for the pesticide Atrazine (ATR) in a controlled soil experiment and in situ in an intact lake sediment core. The soil study explored the relationships between soil solution, DGT measured labile ATR and solvent extractable ATR in dosed soils of different organic matter, pH status and incubation times. The results are further interpreted using the DIFS (DGT-induced fluxes in soils and sediments) model. Resupply of ATR to the soil solution was partially sustained by the solid phase in all the soils. This was due to small labile pool size and slow kinetics, with soil pH being an important controlling factor. The in situ sediment study successfully used a DGT probe to examine labile ATR distribution through the core on the subcm scale. It demonstrated–for the first time–an easy to use in situ technique to investigate the effects of redox on resupply kinetics and biogeochemical processes of trace organic contaminants in sediments.

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