Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O2 during XAS measurements. With strict O2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Estimating Radium Activity in Shale Gas Produced Brine.

Shale gas reservoir-produced brines may contain elevated levels of naturally occurring radioactive material, including Ra-226 and Ra-228, which come from the decay of U-238 and Th-232 in shale. While the total Ra activity in shale gas wastewaters can vary by over 3 orders of magnitude, the parent radionuclides tend to only vary by 1 order of magnitude. The extent of Ra mobilization from the shale into produced brines is thought to be largely controlled by adsorption/desorption from the shale, which is influenced by shale cation exchange capacity (CEC) and reservoir brine salinity, often reported as the total dissolved solids (TDS). To determine how these factors lead to such large variation in Ra activity of produced brines, the U content and CEC of shale samples from the Antrim and Utica-Collingwood shales in Michigan and the Marcellus shale in Pennsylvania were evaluated. Analysis of produced brine from 17 Antrim shale gas wells was then used to develop an empirical relationship between Ra-226 activity and produced water TDS for a given U content of the shale. This correlation will provide an a priori estimate of the expected Ra activity of a produced brine from a given shale gas play when the brine salinity and U content of the shale are known. Such information can serve as a guide for optimal wastewater treatment and disposal strategies prior to any drilling activity, thereby reducing risks associated with elevated Ra activity in shale gas wastewaters.

Rapid Mobilization of Noncrystalline U(IV) Coupled with FeS Oxidation.

The reactivity of disordered, noncrystalline U(IV) species remains poorly characterized despite their prevalence in biostimulated sediments. Because of the lack of crystalline structure, noncrystalline U(IV) may be susceptible to oxidative mobilization under oxic conditions. The present study investigated the mechanism and rate of oxidation of biogenic noncrystalline U(IV) by dissolved oxygen (DO) in the presence of mackinawite (FeS). Previously recognized as an effective reductant and oxygen scavenger, nanoparticulate FeS was evaluated for its role in influencing U release in a flow-through system as a function of pH and carbonate concentration. The results demonstrated that noncrystalline U(IV) was more susceptible to oxidation than uraninite (UO2) in the presence of dissolved carbonate. A rapid release of U occurred immediately after FeS addition without exhibiting a temporary inhibition stage, as was observed during the oxidation of UO2, although FeS still kept DO levels low. X-ray photoelectron spectroscopy (XPS) characterized a transient surface Fe(III) species during the initial FeS oxidation, which was likely responsible for oxidizing noncrystalline U(IV) in addition to oxygen. In the absence of carbonate, however, the release of dissolved U was significantly hindered as a result of U adsorption by FeS oxidation products. This study illustrates the strong interactions between iron sulfide and U(IV) species during redox transformation and implies the lability of biogenic noncrystalline U(IV) species in the subsurface environment when subjected to redox cycling events.

Anaerobic Disposal of Arsenic-Bearing Wastes Results in Low Microbially Mediated Arsenic Volatilization.

The removal of arsenic from drinking water sources produces arsenic-bearing wastes, which are disposed of in a variety of ways. Several disposal options involve anaerobic environments, including mixing arsenic waste with cow dung, landfills, anaerobic digesters, and pond sediments. Though poorly understood, the production of gaseous arsenic species in these environments can be a primary goal (cow dung mixing) or an unintended consequence (anaerobic digesters). Once formed, these gaseous arsenic species are readily diluted in the atmosphere. Arsenic volatilization can be mediated by the enzyme arsenite S-adenosylmethionine methyltransferase (ArsM) or through the enzymes involved in methanogenesis. In this study, methanogenic mesocosms with arsenic-bearing ferric iron waste from an electrocoagulation drinking water treatment system were used to evaluate the role of methanogenesis in arsenic volatilization using methanogen inhibitors. Arsenic volatilization was highest in methanogenic mesocosms, but represented <0.02% of the total arsenic added. 16S rRNA cDNA sequencing, qPCR of mcrA transcripts, and functional gene array-based analysis of arsM expression, revealed that arsenic volatilization correlated with methanogenic activity. Aqueous arsenic concentrations increased in all mesocosms, indicating that unintended contamination may result from disposal in anaerobic environments. This highlights that more research is needed before recommending anaerobic disposal intended to promote arsenic volatilization.

Vinegar-amended anaerobic biosand filter for the removal of arsenic and nitrate from groundwater.

The performance of a vinegar-amended anaerobic biosand filter was evaluated for future application as point-of-use water treatment in rural areas for the removal of arsenic and nitrate from groundwater containing common ions. Due to the importance of sulfate and iron in arsenic removal and their variable concentrations in groundwater, influent sulfate and iron concentrations were varied. Complete removal of influent nitrate (50 mg/L) and over 50% removal of influent arsenic (200 µg/L) occurred. Of all conditions tested, the lowest median effluent arsenic concentration was 88 µg/L. Iron removal occurred completely when 4 mg/L was added, and sulfate concentrations were lowered to a median concentration <2 mg/L from influent concentrations of 22 and 50 mg/L. Despite iron and sulfate removal and the establishment of reducing conditions, arsenic concentrations remained above the World Health Organization's arsenic drinking water standard. Further research is necessary to determine if anaerobic biosand filters can be improved to meet the arsenic drinking water standard and to evaluate practical implementation challenges.

Influence of iron sulfides on abiotic oxidation of UO2 by nitrite and dissolved oxygen in natural sediments.

Iron sulfide precipitates formed under sulfate reducing conditions may buffer U(IV) insoluble solid phases from reoxidation after oxidants re-enter the reducing zone. In this study, sediment column experiments were performed to quantify the effect of biogenic mackinawite on U(IV) stability in the presence of nitrite or dissolved oxygen (DO). Two columns, packed with sediment from an abandoned U contaminated mill tailings site near Rifle, CO, were biostimulated for 62 days with an electron donor (3 mM acetate) in the presence (BRS+) and absence (BRS−) of 7 mM sulfate. The bioreduced sediment was supplemented with synthetic uraninite (UO2(s)), sterilized by gamma-irradiation, and then subjected to a sequential oxidation by nitrite and DO. Biogenic iron sulfides produced in the BRS+ column, mostly as mackinawite, inhibited U(IV) reoxidation and mobilization by both nitrite and oxygen. Most of the influent nitrite (0.53 mM) exited the columns without oxidizing UO2, while a small amount of nitrite was consumed by iron sulfides precipitates. An additional 10-day supply of 0.25 mM DO influent resulted in the release of about 10% and 49% of total U in BRS+ and BRS­ columns, respectively. Influent DO was effectively consumed by biogenic iron sulfides in the BRS+ column, while DO and a large U spike were detected after only a brief period in the effluent in the BRS­ column.

Nano-FeS inhibits UO2 reoxidation under varied oxic conditions.

Bioreductive in situ treatment of U-contaminated groundwater can convert soluble U(VI) species to immobile reduced U(IV) solid phases such as UO2(s) to contain U movement. Once active bioremediation is halted, UO2 may be subsequently reoxidized if oxidants such as oxygen enter the reducing zone. However, iron sulfide minerals that form during bioreduction may serve as electron sources or oxygen scavengers and inhibit UO2 reoxidation upon oxygen intrusion. In this study, flow-through reactor experiments examined the abiotic kinetics of UO2 oxidative dissolution in the presence of oxygen and nanoparticulate FeS as a function of pH, dissolved oxygen (DO) concentration, and FeS content. The UO2 dissolution rates in the presence of FeS were over 1 order of magnitude lower than those in the absence of FeS under otherwise comparable oxic conditions. FeS effectively scavenged DO and preferentially reacted with oxygen, contributing to a largely unreacted UO2 solid phase during an "inhibition period" as determined by X-ray absorption spectroscopy (XAS). The removal of DO by FeS was significant but incomplete during the inhibition period, resulting in surface-oxidation-limited dissolution and greater UO2 dissolution rate with increasing influent DO concentration and decreasing FeS content. Although the rate was independent of solution pH in the range of 6.1-8.1, the length of the inhibition period was shortened by substantial FeS dissolution at slightly acidic pH. The reducing capacity of FeS was greatest at basic pH where surface-mediated FeS oxidation dominated.

Surface passivation limited UO2 oxidative dissolution in the presence of FeS.

Iron sulfide minerals produced during in situ bioremediation of U can serve as an oxygen scavenger to retard uraninite (UO2) oxidation upon oxygen intrusion. Under persistent oxygen supply, however, iron sulfides become oxidized and depleted, giving rise to elevated dissolved oxygen (DO) levels and remobilization of U(IV). The present study investigated the mechanism that regulates UO2 oxidative dissolution rate in a flow-through system when oxygen breakthrough occurred as a function of mackinawite (FeS) and carbonate concentrations. The formation and evolution of surface layers on UO2 were characterized using XAS and XPS. During FeS inhibition period, the continuous supply of carbonate and calcium in the influent effectively complexed and removed oxidized U(VI) to preserve an intermediate U4O9 surface. When the FeS became depleted by oxidization, a transient, rapid dissolution of UO2 was observed along with DO breakthrough in the reactor. This rate was greater than during the preceding FeS inhibition period and control experiments in the absence of FeS. With increasing DO, the rate slowed and the rate-limiting step shifted from surface oxidation to U(VI) detachment as U(VI) passivation layers developed. In contrast, increasing the carbonate concentrations facilitated detachment of surface-associated U(VI) complexes and impeded the formation of U(VI) passivation layer. This study demonstrates the critical role of U(VI) surface layer formation versus U(VI) detachment in controlling UO2 oxidative dissolution rate during periods of variable oxygen presence under simulated groundwater conditions.

Growth of Desulfovibrio vulgaris when respiring U(VI) and characterization of biogenic uraninite.

The capacity of Desulfovibrio vulgaris to reduce U(VI) was studied previously with nongrowth conditions involving a high biomass concentration; thus, bacterial growth through respiration of U(VI) was not proven. In this study, we conducted a series of batch tests on U(VI) reduction by D. vulgaris at a low initial biomass (10 to 20 mg/L of protein) that could reveal biomass growth. D. vulgaris grew with U(VI) respiration alone, as well as with simultaneous sulfate reduction. Patterns of growth kinetics and solids production were affected by sulfate and Fe(2+). Biogenic sulfide nonenzymatically reduced 76% of the U(VI) and greatly enhanced the overall reduction rate in the absence of Fe(2+) but was rapidly scavenged by Fe(2+) to form FeS in the presence of Fe(2+). Biogenic U solids were uraninite (UO2) nanocrystallites associated with 20 mg/g biomass as protein. The crystallite thickness of UO2 was 4 to 5 nm without Fe(2+) but was <1.4 nm in the presence of Fe(2+), indicating poor crystallization inhibited by adsorbed Fe(2+) and other amorphous Fe solids, such as FeS or FeCO3. This work fills critical gaps in understanding the metabolic utilization of U by microorganisms and formation of UO2 solids in bioremediation sites.

Arsenic waste management: a critical review of testing and disposal of arsenic-bearing solid wastes generated during arsenic removal from drinking water.

Water treatment technologies for arsenic removal from groundwater have been extensively studied due to widespread arsenic contamination of drinking water sources. Central to the successful application of arsenic water treatment systems is the consideration of appropriate disposal methods for arsenic-bearing wastes generated during treatment. However, specific recommendations for arsenic waste disposal are often lacking or mentioned as an area for future research and the proper disposal and stabilization of arsenic-bearing waste remains a barrier to the successful implementation of arsenic removal technologies. This review summarizes current disposal options for arsenic-bearing wastes, including landfilling, stabilization, cow dung mixing, passive aeration, pond disposal, and soil disposal. The findings from studies that simulate these disposal conditions are included and compared to results from shorter, regulatory tests. In many instances, short-term leaching tests do not adequately address the range of conditions encountered in disposal environments. Future research directions are highlighted and include establishing regulatory test conditions that align with actual disposal conditions and evaluating nonlandfill disposal options for developing countries.