A paradigm shift for evaluating natural attenuation of radioactive iodine in soils and sediments: Species-specific mechanisms and pathways.

The primary approach to assessing monitored natural attenuation (MNA) is currently based on a conceptual model utilizing the total contaminant concentrations, assuming a single aqueous species. However, many contaminants, such as metals and radionuclide - including iodine, can exist in multiple species that behave chemically differently in the environment and can exist simultaneously. For example, radioiodine often occurs concurrently as three major aqueous species: iodide (I), iodate (IO), and organo-I, which undergo distinct attenuation pathways and exhibit markedly different mobility and geochemical behavior.

Spectral induced polarization of corrosion of sulfur modified Iron in sediments.

Spectral induced polarization (SIP) responses are not well understood within the context of remediation applications at contaminated sites. Systematic SIP studies are needed to gain further insights into the complex electrical response of dynamic, biogeochemical states to enable the use of SIP for subsurface site characterization and remediation monitoring. Although SIP measurements on zero valent iron have been previously published, the SIP response for sulfur modified iron (SMI), a similar potential subsurface reductive amendment, has not yet been reported.

Impact of chromium (VI) as a co-contaminant on the sorption and co-precipitation of uranium (VI) in sediments under mildly alkaline oxic conditions.

Uranium (U) waste, generated at a variety of mines and nuclear production sites, migrates in the subsurface, posing a serious threat to contaminate groundwater systems. In this study, batch equilibrium and kinetic experiments, geochemical modeling and solid phase characterization were conducted to investigate the impact of Cr(VI), a common co-contaminant, on the adsorption of U(VI) to quartz, plagioclase feldspar, and carbonate-dominated sediment (≤2 mm). Batch experiments were performed under slightly alkaline conditions (7.

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment.

In situ remediation applications of ammonia (NH) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH treatment.

Hydrolysis of methylphosphonic anhydride solid to methylphosphonic acid probed by Raman and infrared reflectance spectroscopies.

Much is still unknown about the mechanisms and rates of environmental degradation of organophosphorous pesticides and agents. In this study we focus on the degradation of one organophosphorous compound, namely solid methylphosphonic anhydride [CHP(O)OHOP(O)OHCH, MPAN] and its rate of conversion to methylphosphonic acid (MPA) heterogeneous hydrolysis. Pure MPAN was synthesized and loaded in open sample cups placed inside exposure chambers containing saturated salt solutions to control the relative humidity (RH).

In situ precipitation of hydrous ferric oxide (HFO) for remediation of subsurface iodine contamination.

A practical approach for in situ hydrous ferric oxide (HFO) precipitation was developed for iodine immobilization under field-scale conditions at the Hanford Site. A series of 1D meter-long bench-top column experiments packed with Hanford sediments was conducted with a single acidic ferric solution (0.1 M, pH = 1.

Hybrid Sorbents for I Capture from Contaminated Groundwater.

Radioiodine (I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S.

In situ reductive dissolution to remove Iodine-129 from aquifer sediments.

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford Site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e.

Technetium immobilization by materials through sorption and redox-driven processes: A literature review.

The objective of this review is to evaluate materials for use as a barrier or other deployed technology to treat technetium-99 (Tc) in the subsurface. To achieve this, Tc interactions with different materials are considered within the context of remediation strategies. Several naturally occurring materials are considered for Tc immobilization, including iron oxides and low solubility sulfide phases.

Iodine immobilization by materials through sorption and redox-driven processes: A literature review.

Radioiodine-129 (I) in the subsurface is mobile and limited information is available on treatment technologies. Scientific literature was reviewed to compile information on materials that could potentially be used to immobilize I through sorption and redox-driven processes, with an emphasis on ex-situ processes. Candidate materials to immobilize I include iron minerals, sulfur-based materials, silver-based materials, bismuth-based materials, ion exchange resins, activated carbon, modified clays, and tailored materials (metal organic frameworks (MOFS), layered double hydroxides (LDHs) and aerogels).

Evaluation of materials for iodine and technetium immobilization through sorption and redox-driven processes.

Radioactive iodine-129 (I) and technetium-99 (Tc) pose a risk to groundwater due to their long half-lives, toxicity, and high environmental mobility. Based on literature reviewed in Moore et al. (2019) and Pearce et al.

A review of the behavior of radioiodine in the subsurface at two DOE sites.

Multiple processes affect the fate of the radioactive isotope I in the environment. Primary categories of these processes include electron transfer reactions mediated by minerals and microbes, adsorption to sediments, interactions with organic matter, co-precipitation, and volatilization. A description of dominant biogeochemical processes is provided to describe the interrelationship of these processes and the associated iodine chemical species.

Persistence of chromate in vadose zone and aquifer sediments in Hanford, Washington.

This study of vadose zone and aquifer sediments beneath a former dichromate spill site showed that the persistence of Cr in the sediments and the large differences in released mass and rate was caused by the dissolution of multiple Cr surface phases. Vadose zone sediments contained numerous 1 to 10 μm high solubility calcium chromate crystals, with lesser amounts of unidentified phases indicated by Ba/Cr association in weathered pyroxenes and Ca/Cr association in weathered Ca-rich plagioclase. Most (>90%) of the Cr mass in these vadose zone sediments was readily leached in laboratory columns at high concentrations (up to 187 mg/L Cr) likely from the highly soluble calcium chromate.

Potential for U sequestration with select minerals and sediments via base treatment.

Temporary base treatment is a potential remediation technique for heavy metals through adsorption, precipitation, and co-precipitation with minerals. Manipulation of pH with ammonia gas injection may be especially useful for vadose zone environments as it does not require addition of liquids that would increase the flux towards groundwater. In this research, we conducted laboratory batch experiments to evaluate the changes in uranium mobility and mineral dissolution with base treatments including sodium hydroxide, ammonium hydroxide, and ammonia gas.

Identification of Uranium Minerals in Natural U-Bearing Rocks Using Infrared Reflectance Spectroscopy.

The identification of minerals, including uranium-bearing species, is often a labor-intensive process using X-ray diffraction (XRD), fluorescence, or other solid-phase or wet chemical techniques. While handheld XRD and fluorescence instruments can aid in field applications, handheld infrared (IR) reflectance spectrometers can now also be used in industrial or field environments, with rapid, nondestructive identification possible via analysis of the solid's reflectance spectrum providing information not found in other techniques. In this paper, we report the use of laboratory methods that measure the IR hemispherical reflectance of solids using an integrating sphere and have applied it to the identification of mineral mixtures (i.

Effects of ammonium on uranium partitioning and kaolinite mineral dissolution.

Ammonia gas injection is a promising technique for the remediation of uranium within the vadose zone. It can be used to manipulate the pH of a system and cause co-precipitation processes that are expected to remove uranium from the aqueous phase and decrease leaching from the solid phase. The work presented in this paper explores the effects of ammonium and sodium hydroxide on the partitioning of uranium and dissolution of the kaolinite mineral in simplified synthetic groundwaters using equilibrium batch sorption and sequential extraction experiments.

Ammonia gas transport and reactions in unsaturated sediments: implications for use as an amendment to immobilize inorganic contaminants.

Use of gas-phase amendments for in situ remediation of inorganic contaminants in unsaturated sediments of the vadose zone may be advantageous, but there has been limited development and testing of gas remediation technologies. Treatment with ammonia gas has a potential for use in treating inorganic contaminants (such as uranium) because it induces a high pore-water pH, causing mineral dissolution and subsequent formation of stable precipitates that decrease the mobility of some contaminants. For field application of this treatment, further knowledge of ammonia transport in porous media and the geochemical reactions induced by ammonia treatment is needed.

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.

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e.

Rheological behavior of xanthan gum solution related to shear thinning fluid delivery for subsurface remediation.

Xanthan gum solutions are shear thinning fluids which can be used as delivery media to improve the distribution of remedial amendments injected into heterogeneous subsurface environments. The rheological behavior of the shear thinning solution needs to be known to develop an appropriate design for field injection. In this study, the rheological properties of xanthan gum solutions were obtained under various chemical and environmental conditions relevant to delivery of remedial amendments to groundwater.

Enhanced remedial amendment delivery to subsurface using shear thinning fluid and aqueous foam.

A major issue with in situ subsurface remediation is the ability to achieve an even spatial distribution of remedial amendments to the contamination zones in an aquifer or vadose zone. Amendment delivery to the aquifer using shear thinning fluid and to the vadose zone using aqueous foam has the potential to enhance the distribution. 2-D saturated flow cell experiments were conducted to evaluate the enhanced fluid sweeping over heterogeneous system, improved contaminant removal, and extended amendment presence in low-permeability zones achieved by shear thinning fluid delivery.

Desorption behavior of carbon tetrachloride and chloroform in contaminated low organic carbon aquifer sediments.

Slow release behavior of carbon tetrachloride (CCl(4)) and chloroform (CHCl(3)) in low organic carbon (<0.1%) deep aquifer sediments was quantified by 1-D column desorption studies with intact cores. The compounds had been in contact with the sediments for 30years.

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous FeII solutions.

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE).

Remediating explosive-contaminated groundwater by in situ redox manipulation (ISRM) of aquifer sediments.

In situ chemical reduction of clays and iron oxides in subsurface environments is an emerging technology for treatment of contaminated groundwater. Our objective was to determine the efficacy of dithionite-reduced sediments from the perched Pantex Aquifer (Amarillo, TX) to abiotically degrade the explosives RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene). The effects of dithionite/buffer concentrations, sediments-solution ratios, and the contribution of Fe(II) were evaluated in batch experiments.

Biotic and abiotic degradation of CL-20 and RDX in soils.

The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes.