Passive sampling is a novel method of analyte concentration from the environment that strives to bring greater ease to field sampling regimes than traditional liquid-solid phase extractions (SPE). It is easier to deploy than a Niskin bottle or CTD rosette, and easier to recover than hoisting up dozens of liters of water. Passive sampling also offers the opportunity for wider exploratory studies, as compounds can be selectively extracted back in lab, rather than having to select a particular phase SPE and follow phase-specific elution methods. In this study, Ethylene Vinyl Acetate copolymer (EVA) was used as a marine sorption and collection media. Its efficacy was tested in both ambient munitions sampling for TNT and RDX, and for sulfate in porewaters. For the munitions subset of samples, the interaction between salinity, temperature, and percent acetate composition of the EVA samplers was explored. It was found that salinity had a large increase on Log KEVA from 0-5 PSU, then became nonlinear from 5-34 PSU. The initial increase was present for all EVA types, and the 5-34 PSU subset’s Log KEVA was affected in similar manner between EVA types. Increasing temperature was found to decrease munitions sorption over 5-25˚C, and it was found that EVA80 was the most efficient sorption media out of the EVA subtypes. This is likely due to dipole interactions from the increase in the polar acetate group. An EVA polymer seeded with barium containing organic compounds was tested for efficacy in sulfate precipitation to the film for use in isotopic sulfur measurements. Out of the many barium containing organic compounds selected for testing, barium oxalate was chosen for its efficiency at precipitating and trapping sulfate from the marine environment, while being able to be easily purified by an acid-catalyzed hydrolysis procedure. It was also proven that the EVA sampler does not add an isotopic bias through fractionation during precipitation to the film from the environment. Overall, it was proven that the Ethylene Vinyl Acetate copolymer is an effective passive sorption media for marine systems, for both munitions compounds and inorganic sulfate.

Monitoring pollutants in air, soil and water is a routine requirement in the workplace, and in the wider environment. Passive samplers can provide a representative picture of levels of pollutants over a period of time from days to months by measuring the average concentrations to which they have been exposed. Air monitors are widely used, for instance to measure the exposure of workers to volatile compounds, but also for monitoring the fate of pollutants in the atmosphere. Passive sampling devices are now becomining increasingly used to monitor pollutants in rivers, coastal waters and ground water where contamination results from sources such as domestic and industrial discharges, and the use of agrochemicals. Passive Sampling Techniques in Environmental Monitoring provides a timely collection of information on a set of techniques that help monitor the quality of air, surface and ground waters. Passive sampling can provide an inexpensive means of obtaining a representative picture of quality over a period of time, even where levels of pollutants fluctuate due to discontinuous discharges or seasonal application of chemicals such as pesticides. Recent changes in legislation have increased the pressure to obtain better information than that provided by classical infrequent spot sampling.Brought together in one source, this book looks at the performance of a range of devices for the passive sampling of metals, and of non-polar and polar organic chemicals in air and in water. The strengths and weaknesses and the range of applicability of the technology are considered. * Comprehensive review of passive sampling - covering air, water and majority of available technologies in one volume* Chapters written by international specialist experts * Covers theory and applications, providing background information and guidelines for use in the field

The primary goal of this dissertation was to develop and evaluate an improved aquatic passive sampling device (PSD) for measurement of polar organic contaminants. Chemical uptake of current polar-PSDs (e.g., POCIS - polar organic chemical integrative sampler) is dependent on the specific environmental conditions in which the sampler is deployed (flow-rate, temperature), leading to large uncertainties when applying laboratory-derived sampling rates in-situ. A novel configuration of the diffusive gradients in thin-films (DGT) passive sampler was developed to overcome these challenges. The organic-DGT (o-DGT) configuration comprised a hydrophilic-lipophilic balance® sorbent binding phase and an outer agarose diffusive gel (thickness = 0.5-1.5 mm), notably excluding a polyethersulfone protective membrane which is used with all other polar-PSDs. Sampler calibration exhibited linear uptake and sufficient capacity for 34 pharmaceuticals and pesticides over typical environmental deployment times, with measured sampling rates ranging from 9-16 mL/d. Measured and modelled diffusion coefficients (D) through the outer agarose gel provided temperature-specific estimates of o-DGT sampling rates within 20% (measured-D) and 30% (modelled-D) compared to rates determined through full-sampler calibration. Boundary layer experiments in lab and field demonstrated that inclusion of the agarose diffusive gel negated boundary layer effects, suggesting that o-DGT uptake is largely insensitive to hydrodynamic conditions. The utility of o-DGT was evaluated under a variety of field conditions and performance was assessed in comparison to POCIS and grab samples. o-DGT was effective at measuring pharmaceuticals and pesticides in raw wastewater effluents, small creeks, large fast-flowing rivers, open-water lakes, and under ice at near-zero water temperatures. Concentrations measured by o-DGT were more accurate than POCIS when compared to grab samples, likely resulting from the influence in-situ conditions have on POCIS. Modelled sampling rates were successfully used to estimate semi-quantitative water concentrations of suspect wastewater contaminants using high-resolution mass spectrometry, demonstrating the unique utility of this o-DGT technique. This dissertation establishes o-DGT as a more accurate, user-friendly, and widely applicable passive sampler compared to current-use polar-PSDs. The o-DGT tool will help facilitate more accurate and efficient monitoring efforts and ultimately lead to more appropriate exposure data and environmental risk assessment.

Contaminants can exist in a wide range of states in aqueous environments, especially in surface waters. They can be freely dissolved or associated with dissolved or particulate organic matter depending on their chemical and physical characteristics. The freely dissolved fraction represents the most bioavailable fraction to an organism. These freely dissolved contaminants can cross biomembranes, potentially exerting toxic effects. Passive sampling devices (PSDs) have been developed to aid in sampling many of these contaminants by having the ability to distinguish between the freely dissolved and bound fraction of a contaminant. A new PSD, the Lipid-Free Tube (LFT) sampler was developed in response to some of the shortcomings of other current PSD that sample hydrophobic organic contaminants (HOCs). The device and laboratory methods were original modeled after a widely utilized PSD, the semipermeable membrane device (SPMD), and then improved upon. The effectiveness, efficiency, and sensitivity of not only the PSD itself, but also the laboratory methods were investigated. One requirement during LFT development was to ensure LFTs could be coupled with biological analyses without deleterious results. In an embryonic zebrafish developmental toxicity assay, embryos exposed to un-fortified LFT extracts did not show significant adverse biological response as compared to controls. Also, LFT technology lends itself to easy application in monitoring pesticides at remote sampling sites. LFTs were utilized during a series of training exchanges between Oregon State University and the Centre de Recherches en Ecotoxicologie pour le Sahel (CERES)/LOCUSTOX laboratory in Dakar, Senegal that sought to build "in country" analytical capacity. Application of LFTs as biological surrogates for predicting potential human health risk endpoints, such as those in a public health assessment was also investigated. LFT mass and accumulated contaminant masses were used directly, representing the amount of contaminants an organism would be exposed to through partitioning assuming steady state without metabolism. These exposure concentrations allow for calculating potential health risks in a human health risk model. LFT prove to be a robust tool not only for assessing bioavailable water concentrations of HOCs, but also potentially providing many insights into the toxicological significance of aquatic contaminants and mixtures.

A passive sampling method applicable to personnel and area monitoring has been developed for the quantitation of hydrazine, monomethylhydrazine (MMH), and unsymmetrical dimethylhydrazine (UDMH) in ambient air at the part-per-billion (ppb) level. The method uses a black molded low density polyethylene badge consisting of a diffusion barrier and a citric acid collection medium. It collects samples that can be analyzed by the NIOSH colorimetric method or a coulometric titration procedure. The two millimeter thick diffusion barrier contains 144 one millimeter diameter holes and produces a collection rate for MMH of approximately 27 ml/min. The accuracy of data collected with this badge is within 30% of actual values. The dosimeter has demonstrated accuracy for sampling periods of 15 minutes to 66 hours, when sampling MMH at the threshold limit value (TLV) concentration of 200 ppb. The limits of detection are dictated by the specific analytical method. Coulometric titration will detect exposures of 30 ppb-hours. An evaluation of the effects of face velocity, relative humidity, and potential interferences was conducted. (jes).