A successful anaerobic bioaugmentation was carried out
on a trichloroethene (TCE)-contaminated aquifer at
Dover Air Force Base, DE, using a microbial enrichment
culture capable of dechlorinating TCE to ethene. A
hydraulically controlled pilot system 12 × 18 m was
constructed 15 m below ground surface in an alluvial
aquifer to introduce nutrients and substrate into the
groundwater. Ambient TCE and cis-1,2-dichloroethene
(cDCE) concentrations in groundwater averaged 4800 and
1200 μg/L. The pilot operated for 568 days. Results by
day 269 confirmed previous laboratory work showing that
dechlorination did not proceed past cDCE. By this time,
most of the TCE was dechlorinated to cDCE, and cDCE was
the predominant contaminant. An ethene-forming microbial
enrichment culture from the Department of Energy's
Pinellas site in Largo, FL, was injected into the pilot area.
After a lag period of about 90 days, vinyl chloride and
ethene began to appear in wells. The injected culture
survived and was transported through the pilot area. By day
509, TCE and cDCE were fully converted to ethene.
Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.
Phosphate is an essential nutrient for life on Earth, present in adenosine triphosphate (ATP), deoxyribonucleic acid (DNA), ribonucleic acid (RNA), and phospholipid membranes. Phosphorus does not have a significant volatile phase, and its release from minerals is therefore critical to its bioavailability. Organic ligands can enhance phosphate release from minerals relative to release in inorganic solutions, and phosphorus depletion in paleosols has consequently been used as a signature of the presence of ligands secreted by terrestrial organisms on early Earth. We performed batch dissolution experiments of the Mars-relevant phosphate minerals merrillite, whitlockite, chlorapatite, and fluorapatite in solutions containing organic compounds relevant to Mars. We also analyzed these phosphate minerals using the ChemCam laboratory instrument at Los Alamos, providing spectra of end-member phosphate phases that are likely present on the surface of Mars. Phosphate release rates from chlorapatite, whitlockite, and merrillite were enhanced by mellitic, oxalic, succinic, and acetic acids relative to inorganic controls by as much as >35 × . The effects of the organic compounds could be explained by the denticity of the ligand, the strength of the complex formed with calcium, and the solution saturation state. Merrillite, whitlockite, and chlorapatite dissolution rates were more strongly enhanced by acetic and succinic acids relative to inorganic controls (as much as >10 ×) than were fluorapatite dissolution rates (≲2 ×). These results suggest that depletion of phosphate in soils, rocks or sediments on Mars could be a sensitive indicator of the presence of organic compounds.
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