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USGS2007

Thioarsenates in geothermal waters of Yellowstone National Park: Determination, preservation, and geochemical importance

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCl addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.

Wyoming↗

USGS1999

Nevada STORMS project: Measurement of mercury emissions from naturally enriched surfaces

Diffuse anthropogenic and naturally mercury-enriched areas represent long-lived sources of elemental mercury to the atmosphere. The Nevada Study and Tests of the Release of Mercury From Soils (STORMS) project focused on the measurement of mercury emissions from a naturally enriched area. During the project, concurrent measurements of mercury fluxes from naturally mercury-enriched substrate were made September 1–4, 1997, using four micrometeorological methods and seven field flux chambers. Ambient air mercury concentrations ranged from 2 to nearly 200 ng m −3 indicating that the field site is a source of atmospheric mercury. The mean daytime mercury fluxes, during conditions of no precipitation, measured with field chambers were 50 to 360 ng m −2 h −1 , and with the micrometeorological methods were 230 to 600 ng m −2 h −1 . This wide range in mercury emission rates reflects differences in method experimental designs and local source strengths. Mercury fluxes measured by many field chambers were significantly different ( p <0.05) but linearly correlated. This indicates that field chambers responded similarly to environmental conditions, but differences in experimental design and site heterogeneity had a significant influence on the magnitude of mercury fluxes. Data developed during the field study demonstrated that field flux chambers are ideal for assessment of the physicochemical processes driving mercury flux and development of an understanding of the magnitude of the influence of individual factors on flux. In general, mean mercury fluxes measured with micrometeorological methods during daytime periods were nearly 3 times higher than mean fluxes measured with field flux chambers. Micrometeorological methods allow for derivation of a representative mercury flux occurring from an unconstrained system and provide an assessment of the actual magnitude and variability of fluxes occurring from an area.

Journal of Geophysical Research D: Atmospheres↗