ALBERT

Description: We report experimental evidences to support a new formation mechanism, multiphase redox plasma chemistry, for perchlorate on Mars observed during the Phoenix mission, whose high concentrations and high ClO4/Cl ratio cannot be fully interpreted by photochemistry. This chemical reaction occurs between Cl-bearing minerals on the Mars surface and free radicals generated by electrostatic discharge (ESD) during Mars dust events (dust storms, dust devils, and grain saltation). We conducted simulated ESD experiments in a Mars chamber with pure CO2, CO2+H2O(g), and Mars Simulate Gas Mixture at Martian atmospheric pressure. We directly observed (1) the instantaneous generation of atmospheric free radicals CO2+, CO+, OI, HIII, HII, OH, ArI, N2, and N2+in normal glow discharge (NGD), detected by in situ plasma emission spectroscopy, and O3by UV and Mid-IR spectroscopy; (2) the fast transformation of NaCl to NaClO3and NaClO4detected by laser Raman spectroscopy, with oxychlorine enrichment at the sample surfaces confirmed by ion chromatography. Through two sets of experimental comparison, we found that the oxidation power of ESD-electron is three orders of magnitude higher than that of UVC-photon. We scaled our experimental results to the modeled ESD in Mars dust events and Mars surface UV radiation level, and concluded that plasma chemistry occurred during Mars dust events can be an additional important formation mechanism for the large amounts of perchlorates observed during various missions to Mars.

Description: 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.