Influence of alkaline co-contaminants on technetium mobility in vadose zone sediments.

Pertechnetate was slowly reduced in a natural, untreated arid sediment under anaerobic conditions (0.02 nmolg(-1)h(-1)), which could occur in low permeability zones in the field, most of which was quickly oxidized. A small portion of the surface Tc may be incorporated into slowly dissolving surface phases, so was not readily oxidized/remobilized into pore water. In contrast, pertechnetate reduction in an anaerobic sediment containing adsorbed ferrous iron as the reductant was rapid (15-600 nmolg(-1)h(-1)), and nearly all (96-98%) was rapidly oxidized/remobilized (2.6-6.8 nmolg(-1)h(-1)) within hours. Tc reduction in an anaerobic sediment containing 0.5-10mM sulfide showed a relatively slow reduction rate (0.01-0.03 nmolg(-1)h(-1)) that was similar to observations in the natural sediment. Pertechnetate infiltration into sediment with a highly alkaline water resulted in rapid reduction (0.07-0.2 nmolg(-1)h(-1)) from ferrous iron released during biotite or magnetite dissolution. Oxidation of NaOH-treated sediments resulted in slow Tc oxidation (∼0.05 nmolg(-1)h(-1)) of a small fraction of the surface Tc (13-23%). The Tc remaining on the surface was Tc(IV) (by XANES), and autoradiography and elemental maps of Tc (by electron microprobe) showed Tc was present associated with specific minerals, rather than being evenly distributed on the surface. Dissolution of quartz, montmorillonite, muscovite, and kaolinite also occurred in the alkaline water, resulting in significant aqueous silica and aluminum. Over time, aluminosilicates, cancrinite, zeolite and sodalite were precipitating. These precipitates may be coating surface Tc(IV) phases, limiting reoxidation.

Imaging wellbore cement degradation by carbon dioxide under geologic sequestration conditions using X-ray computed microtomography.

X-ray microtomography (XMT), a nondestructive three-dimensional imaging technique, was applied to demonstrate its capability to visualize the mineralogical alteration and microstructure changes in hydrated Portland cement exposed to carbon dioxide under geologic sequestration conditions. Steel coupons and basalt fragments were added to the cement paste in order to simulate cement-steel and cement-rock interfaces. XMT image analysis showed the changes of material density and porosity in the degradation front (density: 1.98 g/cm(3), porosity: 40%) and the carbonated zone (density: 2.27 g/cm(3), porosity: 23%) after reaction with CO(2)-saturated water for 5 months compared to unaltered cement (density: 2.15 g/cm(3), porosity: 30%). Three-dimensional XMT imaging was capable of displaying spatially heterogeneous alteration in cement pores, calcium carbonate precipitation in cement cracks, and preferential cement alteration along the cement-steel and cement-rock interfaces. This result also indicates that the interface between cement and host rock or steel casing is likely more vulnerable to a CO(2) attack than the cement matrix in a wellbore environment. It is shown here that XMT imaging can potentially provide a new insight into the physical and chemical degradation of wellbore cement by CO(2) leakage.

Growth inhibition and stimulation of Shewanella oneidensis MR-1 by surfactants and calcium polysulfide.

Foam delivery technology (FDT) uses surfactant based foam to immobilize subsurface contaminants in situ. Where traditional approaches are impractical, FDT has the potential to overcome many of the technical challenges facing the remediation of contaminated deep vadose zone environments. However, little is known about the effects these reactive chemicals may have on microorganisms inhabiting the contaminated subsurface. In addition, there are currently no standard assays to assess microbial responses to subsurface remedial treatments while these agents are under development. The objective of this study was to develop a rapid laboratory assay to assess the potential growth inhibition and/or stimulation of microorganisms following exposure to candidate FDT components. Calcium polysulfide (CPS) and several surfactants (i.e. sodium laureth sulfate (SLES), sodium dodecyl sulfate (SDS), cocamidopropyl betaine (CAPB) and NINOL40-CO) have diverse chemistries and are candidate components of FDT. Shewanella oneidensis MR-1 cultures were exposed to a range of concentrations of these chemicals to determine the minimum bactericidal concentration (MBC) and the growth and viability potential of these components. Concentrations of SDS higher than 700 µM were toxic to S. oneidensis MR-1 growth over the course of four days of exposure. The relative acute toxicity order for these compounds was SDS >> CPS >> NINOL 40-CO>SLES≥CAPB. Dose dependent growth decreases (20-100mM) were observed in the CAPB and SLES treated cultures and both CPS and NINOL 40-CO were toxic at all concentrations tested (1.45-7.25 mM CPS). Both SLES (20-100mM) and SDS at lower concentrations (20-500 µM) were stimulatory to S. oneidensis MR-1 indicating a capacity to be used as a carbon source. These studies also identified potentially key component characteristics, such as precipitate formation and oxygen availability, which may prove valuable in assessing the response of subsurface microorganisms. This benchtop system provides a capability to assess adverse microbial-remediation responses and contributes to the development of in situ remedial chemistries before they are deployed in the field.