A review of peeper passive sampling approaches to measure the availability of inorganics in sediment porewater.

Sediment porewater dialysis passive samplers, also known as "peepers," are inert containers with a small volume of water (usually 1-100 mL) capped with a semi-permeable membrane. When exposed to sediment over a period of days to weeks, chemicals (typically inorganics) in sediment porewater diffuse through the membrane into the water. Subsequent analysis of chemicals in the peeper water sample can provide a value that represents the concentrations of freely-dissolved chemicals in sediment, a useful measurement for understanding fate and risk. Despite more than 45 years of peeper uses in peer-reviewed research, there are no standardized methods available, which limits the application of peepers for more routine regulatory-driven decision making at sediment sites. In hopes of taking a step towards standardizing peeper methods for measuring inorganics in sediment porewater, over 85 research documents on peepers were reviewed to identify example applications, key methodological aspects, and potential uncertainties. The review found that peepers could be improved by optimizing volume and membrane geometry to decrease the necessary deployment time, decrease detection limits, and provide sufficient sample volumes needed for commercial analytical laboratories using standardized analytical methods. Several methodological uncertainties related to the potential impact of oxygen presence in peeper water prior to deployment and oxygen accumulation in peepers after retrieval from sediment were noted, especially for redox-sensitive metals. Additional areas that need further development include establishing the impact of deionized water in peeper cells when used in marine sediment and use of pre-equilibration sampling methods with reverse tracers allowing shorter deployment periods. Overall, it is expected that highlighting these technical aspects and research needs will encourage work to address critical methodological challenges, aiding in the standardization of peeper methods for measuring porewater concentrations at contaminated regulatory-driven sediment sites.

The development of diffusive equilibrium, high-resolution passive samplers to measure perfluoroalkyl substances (PFAS) in groundwater.

Per- and poly-fluoroalkyl substances (PFAS) are a group of anthropogenic, highly recalcitrant organic compounds consisting of thousands of individual species that are of increasing importance as groundwater contaminants. In-situ measurements of PFAS would be useful to better understand vertical profiles and mobility, contamination in partially saturated media, and to reduce sampling artifacts associated with groundwater collection and analysis. Diffusive equilibrium, high-resolution passive samplers (HRPPs) can be directly driven (>10 m) in sediments or groundwater. The samplers equilibrate with porewater through diffusion across the sampler membrane, providing high spatial resolution (sample every 20 cm) porewater concentrations of dissolved species. The objective of this study was to develop an HRPP to measure PFAS in contaminated groundwater and saturated media. To achieve this objective, a screening study was conducted to demonstrate quantitative measurement of selected PFAS as well as the kinetics of uptake into a sampler using both nylon and stainless steel membranes. Utilizing the results of the screening study, a prototype sampler was demonstrated in a laboratory flow box. Over a deployment period of 28 days, concentrations of several perfluoroalkyl carboxylic acids (PFCAs), a perfluoroalkyl sulfonate (PFSA), and a precursor PFAS reached equilibrium with porewater (sampler concentration >90 percent of porewater concentration). Application of these samplers could provide improved understanding of the behavior of PFAS in saturated or partially saturated groundwater systems and allow better assessment of fate and transport in the subsurface. Reliable subsurface site characterization will yield robust site assessments, conceptual models, and improve remediation designs as well as increase confidence in post remedial assessments at PFAS-impacted locations.