A novel in-situ Raman spectroscopic cell for aqueous geochemistry at the solid-liquid interface.

In-situ Raman spectroscopy has the potential to be a powerful technique for monitoring geochemical reactions at a solid-liquid interface in real time. In this article, we present the development and testing of an in-situ Raman spectroscopic cell, which can be used for reaction systems at moderate temperatures and pressure [<1000 psi (6.89 MPa), <100 °C, relevant to subsurface geologic systems] and can hold samples large enough for chemical mapping of heterogeneous rock surfaces. The system is validated by measuring the temperature-dependent conversion of gypsum to calcite over time. Near total conversion of gypsum to calcite on the mineral surface took 29 hours at room temperature and 150 minutes at 100 °C, corresponding to an 11.6-fold increase in the conversion rate. We anticipate that this cell can be an important tool in quantifying the rates of carbon mineralization relevant to geologic carbon sequestration, particularly for the elevated rates recently observed in mafic/ultramafic rocks.

Gas diffusion through variably-water-saturated zeolitic tuff: Implications for transport following a subsurface nuclear event.

Noble gas transport through geologic media has important applications in the characterization of underground nuclear explosions (UNEs). Without accurate transport models, it is nearly impossible to distinguish between xenon signatures originating from civilian nuclear facilities and UNEs. Understanding xenon transport time through the earth is a key parameter for interpreting measured xenon isotopic ratios. One of the most challenging aspects of modeling gas transport time is accounting for the effect of variable water saturation of geological media. In this study, we utilize bench-scale laboratory experiments to characterize the diffusion of krypton, xenon, and sulfur hexafluoride (SF6) through intact zeolitic tuff under different saturations. We demonstrate that the water in rock cores with low partial saturation dramatically affects xenon transport time compared to that of krypton and SF6 by blocking sites in zeolitic tuff that preferentially adsorb xenon. This leads to breakthrough trends that are strongly influenced by the degree of the rock saturation. Xenon is especially susceptible to this phenomenon, a finding that is crucial to incorporate in subsurface gas transport models used for nuclear event identification. We also find that the breakthrough of SF6 diverges significantly from that of noble gases within our system. When developing field scale models, it is important to understand how the behavior of xenon deviates from chemical tracers used in the field, such as SF6 (Carrigan et al., 1996). These new insights demonstrate the critical need to consider the interplay between rock saturation and fission product sorption during transport modeling, and the importance of evaluating specific interactions between geomedia and gases of interest, which may differ from geomedia interactions with chemical tracers.

Iodine effective diffusion coefficients through volcanic rock: Influence of iodine speciation and rock geochemistry.

Accurate prediction of the subsurface transport of iodine species is important for the assessment of long-term nuclear waste repository performance, as well as monitoring compliance with the Comprehensive Nuclear-Test-Ban Treaty, given that radioiodine decays into radioxenon. However, the transport of iodine through intact geologic media is not well understood, compromising our ability to assess risk associated with radioiodine migration. The current study's goal is to quantify the matrix diffusion of iodine species through saturated volcanic rock, with particular attention paid to the redox environment and potential speciation changes. Diffusion experiments were run for iodide through lithophysae-rich lava, lithophysae-poor lava, and welded tuff, whereas iodate diffusion was studied through welded tuff. Iodine transport was compared with a conservative tracer, HDO, and effective diffusion coefficients were calculated. Likely due to a combination of size and anion exclusion effects, iodine species diffused more slowly than the conservative tracer through all rock types tested. Furthermore, oxidation of iodide to iodate was observed in the lithophysae-poor lava, affecting transport. Results provide much needed data for subsurface transport models that predict radioiodine migration from underground sources, and indicate the pressing need for geochemical and redox interactions to be incorporated into these models.

Trihalomethane precursor reactivity changes in drinking water treatment unit processes during a storm event.

Source water quality can significantly impact the efficacy of water treatment unit processes and the formation of chlorinated and brominated trihalomethanes (THMs). Current water treatment plant performance models may not accurately capture how source water quality variations, such as organic matter variability, can impact treatment unit processes. To investigate these impacts, a field study was conducted wherein water samples were collected along the treatment train for 72 hours during a storm event. Systematic sampling and detailed analyses of water quality parameters, including non-purgeable organic carbon (NPOC), UV absorbance, and THM concentrations, as well as chlorine spiking experiments, reveal how the THM formation potential changes in response to treatment unit processes. Results show that the NPOC remaining after treatment has an increased reactivity towards forming THMs, and that brominated THMs form more readily than chlorinated counterparts in a competitive reaction. Thus both the reactivity and quantity of THM precursors must be considered to maintain compliance with drinking water standards, a finding that should be incorporated into the development of model-assisted treatment operation and optimization. Advanced granular activated carbon (GAC) treatment beyond conventional coagulation-flocculation-sedimentation processes may also be necessary to remove the surge loading of THM-formation precursors during a storm event.

Improving arsenopyrite oxidation rate laws: implications for arsenic mobilization during aquifer storage and recovery (ASR).

Aquifer storage and recovery (ASR) and aquifer recharge (AR) provide technical solutions to address water supply deficits and growing future water demands. Unfortunately, the mobilization of naturally present arsenic due to ASR/AR operations has undermined its application on a larger scale. Predicting arsenic mobility in the subsurface during ASR/AR is further complicated by site-specific factors, including the arsenic mobilization mechanisms, groundwater flow conditions, and multi-phase geochemical interactions. In order to ensure safe and sustainable ASR/AR operation, a better understanding of these factors is needed. The current study thus aims to better characterize and model arsenic remobilization at ASR/AR sites by compiling and analyzing available kinetic data on arsenic mobilization from arsenopyrite under different aqueous conditions. More robust and widely applicable rate laws are developed for geochemical conditions relevant to ASR/AR. Sensitivity analysis of these new rate laws gives further insight into the controlling geochemical factors for arsenic mobilization. When improved rate laws are incorporated as the inputs for reactive transport modeling, arsenic mobilization in ASR/AR operations can be predicted with an improved accuracy. The outcomes will be used to guide groundwater monitoring and specify ASR/AR operational parameters, including water pretreatment requirements prior to injection.

Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.

Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

Different arsenate and phosphate incorporation effects on the nucleation and growth of iron(III) (Hydr)oxides on quartz.

Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration (Rg) of heterogeneously formed precipitates grew from 1.5 to 2.5 (± 1.0) nm within 1 h. For the system containing 10(-5) M arsenate, Rg grew from 3.6 to 6.1 (± 0.5) nm, and for the system containing 10(-5) M phosphate, Rg grew from 2.0 to 4.0 (± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new findings are important because differences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

Water chemistry impacts on arsenic mobilization from arsenopyrite dissolution and secondary mineral precipitation: implications for managed aquifer recharge.

Managed aquifer recharge (MAR) is a water reuse technique with the potential to meet growing water demands. However, MAR sites have encountered arsenic mobilization resulting from recharge operations. To combat this challenge, it is imperative to identify the mechanisms of arsenic mobilization during MAR. In this bench-scale study, arsenic mobilization from arsenopyrite (FeAsS) was characterized for conditions relevant to MAR operations. Experimentally determined activation energies for arsenic mobilization from FeAsS under aerobic conditions were 36.9 ± 2.3 kJ/mol for 10 mM sodium chloride, 40.8 ± 3.5 kJ/mol for 10 mM sodium nitrate, and 43.6 ± 5.0 kJ/mol for secondary effluent from a wastewater treatment plant. Interestingly, the sodium chloride system showed higher arsenic mobilization under aerobic conditions. In addition, secondary mineral precipitation varied among systems and further affected arsenic mobilization. For example, the wastewater system inhibited precipitation, while in the sodium chloride system, faster phase transformation of iron(III) (hydr)oxide precipitates was observed, resulting in hematite formation after 7 days. The phase transformation to hematite will result in less available surface area for arsenic attenuation. These new observations and activation energies can be useful to develop improved reactive transport models for the fate of arsenic during MAR, and develop strategies to minimize arsenic release.

Control of heterogeneous Fe(III) (hydr)oxide nucleation and growth by interfacial energies and local saturations.

To predict the fate of aqueous pollutants, a better understanding of heterogeneous Fe(III) (hydr)oxide nucleation and growth on abundant mineral surfaces is needed. In this study, we measured in situ heterogeneous Fe(III) (hydr)oxide nucleation and growth on quartz, muscovite, and corundum (Al2O3) in 10(-4) M Fe(III) solution (in 10 mM NaNO3 at pH = 3.7 ± 0.2) using grazing incidence small-angle X-ray scattering (GISAXS). Interestingly, both the fastest heterogeneous nucleation and slowest growth occurred on corundum. To elucidate the mechanisms, zeta potential and water contact angle measurements were conducted. Electrostatic forces between the charged Fe(III) (hydr)oxide polymeric embryos and substrate surfaces-which affect local saturations near the substrate surfaces-controlled heterogeneous growth rates. Water contact angles (7.5° ± 0.7, 22.8° ± 1.7, and 44.8° ± 3.7 for quartz, muscovite, and corundum, respectively) indicate that corundum has the highest substrate-water interfacial energy. Furthermore, a comparison of structural mismatches between the substrates and precipitates indicates a lowest precipitate-substrate interfacial energy for corundum. The fastest nucleation on corundum suggests that interfacial energies in the solution-substrate-precipitate system controlled heterogeneous nucleation rates. The unique information provided here bolsters our understanding of nanoparticle-mineral surface interactions, mineral surface modification by iron oxide coating, and pollutant transport.

Arsenic mobilization and attenuation by mineral-water interactions: implications for managed aquifer recharge.

Managed aquifer recharge (MAR) has potential for addressing deficits in water supplies worldwide. It is also widely used for preventing saltwater intrusion, maintaining the groundwater table, and augmenting ecological stream flows, among many other beneficial environmental applications. However, field MAR sites have experienced arsenic mobilization from aquifer formation minerals due to induced changes in groundwater chemistry. To address this environmental concern, it is crucial to understand the potential sources and sinks impacting arsenic mobilization. This paper outlines important mineral-water interactions that can occur at MAR sites. Detailed information on minerals of concern, physiochemical processes for arsenic mobilization or attenuation, and the potential impact of microbial activity and hydrology on these processes is provided. Based on these mineral-water interactions, guidelines for predicting arsenic mobility are presented, and recommendations are made concerning MAR site monitoring. The review emphasizes important aspects in correlating interfacial reactions to reactive transport modeling and elucidating future challenges, a first step toward developing safer and more sustainable MAR operations.