Dissertation/Thesis Abstract

Tungsten speciation, mobilization, and sequestration: Thiotungstate stability constants and examination of (thio)tungstate geochemistry in estuarine waters and sediments
by Mohajerin Haug, Tahmineh Jade, Ph.D., Tulane University School of Science and Engineering, 2014, 168; 3680830
Abstract (Summary)

This dissertation combines laboratory experiments and analysis of field samples to examine tungsten (W) geochemistry. Data from low ionic strength experimental solutions at room temperature containing between 0.01 M to 0.0002 M total sulfide and 0.0027 M - 0.0001 M tungstate were analyzed using UV/VIS spectrophotometry. Stability constants have been determined for the formation of mono-thiotungstate log K01= 3.43 ± 0.61, di-thiotungstate log K12 = 3.02 ± 0.61, tri-thiotungstate log K23 = 2.82 ± 0.02, and we estimated the tetra-thiotungstate log K34 ~ 2.34. Analysis of W, Mo, Mn, and Fe concentrations in estuarine surface and pore waters and sediments captured environmental samples from oxic and sulfidic conditions. Both surface waters and sediments demonstrated a positive correlation between W and Fe. Unlike Mo, which was depleted in sulfidic salt marsh pore waters, W was enriched in all pore waters in comparison to overlying waters. Thermodynamic modeling of W and Mo thioanion species in sulfidic pore water samples predicts ≤ 50% of tungstate (WO4 2-) forms thiotungstate species and complete conversion of molybdate (MoO42-) to tetrathiomolybdate (oO4 2-). Unlike tetrathiomolydate that is known to be more particle reactive than molybdate, increases in dissolved W coincide with increases in dissolved sulfide in pore waters, suggesting thiotungstates are less particle reactive than thiomolybdates at circum-neutral pH. Finally, sediment analysis suggests sequestration of W is dependent on surface water salinity in the intermediate marsh sediments, and long-term W entrapment occurs in sulfidic salt marsh sediments.

Indexing (document details)
Advisor: Johannesson, Karen H.
Commitee: Datta, Saugata, Flowers, George C., Helz, George R.
School: Tulane University School of Science and Engineering
Department: Earth and Environmental Sciences
School Location: United States -- Louisiana
Source: DAI-B 76/06(E), Dissertation Abstracts International
Subjects: Environmental science, Geochemistry
Keywords: Degree of trace metal pyritization, Thiotungstate stability constants, Trace elements in estuarine waters, Tungsten and molybdenum, Tungsten speciation
Publication Number: 3680830
ISBN: 978-1-321-53198-5
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