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Lead(IV) oxide (PbO 2 ) is an important component of the scale in many lead pipes used for water supply. Promoting conditions that maintain its stability could be an effective method for limiting lead release. In this study, we applied a method that combined electrochemical and free chlorine conditioning to form PbO 2 scales on coupons. Lead coupons were then used to investigate the impacts of water stagnation time and residual free chlorine on PbO 2 stability. Free chlorine depletion and associated lead release were investigated from 30 min to 5 days for different initial free chlorine concentrations (0.5-3.0 mg/L as Cl 2 ). There was a lag time of up to 24 h between free chlorine depletion and observed lead increases. With daily readjustment of free chlorine to 0.2 mg/L or higher, the stability of the PbO 2 scale on the lead coupon was maintained and dissolved lead remained consistently below 10 μg/L. This study provides information on key factors affecting reductive dissolution of PbO 2 present in lead scales. It bridges the theoretical threshold free chlorine to maintain PbO 2 stability with experimental results and provides implications for actual water quality monitoring and household drinking water use.

In response to stresses on water demands, some regions augment conventional drinking water sources with alternative water supplies such as desalinated seawater and reclaimed wastewater. The advanced treatment of wastewater by reverse osmosis, microfiltration, and advanced oxidation processes can produce high quality water for potable uses. However, if not appropriately stabilized, the resulting water can be corrosive to metal-based distribution pipes and plumbing materials. We conducted long-term premise plumbing pipe loop experiments with copper pipes containing lead solder to test the impact of the introduction of advanced treated water on the water quality. Advanced treated water (ATW) originally at low pH (<7) and low alkalinity (<10 mg/L as CaCO 3 ) was stabilized with a calcite contactor before being blended with baseline ground water (BLW). The effects of percentages of ATW on the release of lead and copper and on the changes in the microbial diversity were monitored. Experiments monitored metal release from pipes receiving (1) only BLW, (2) a series of blends of BLW and ATW that gradually increased from 25 % to 100 % ATW, and (3) an abrupt switch from BLW to 100 % ATW. Introducing 100 % ATW dramatically increased lead release and simultaneously decreased copper release. Pipe scale analysis showed that the introduction of ATW had destabilized sulfate-containing pipe scales, which exposed the copper pipe surface to galvanic corrosion. The dissolution of scale material was associated with a significant decrease in sulfate concentration in the 100 % ATW which was in agreement with theoretical solubility calculations. The impact of blending ATW on microbial diversity was studied via 16S rRNA gene amplicon sequencing. The composition of the microbial communities changed significantly after water was in contact with the copper pipes in experiments with both BLW and ATW. The type of water recirculating in the pipes affected the structure of the microbial community. The results from this study can be useful for water utilities that are considering potable reuse as they develop strategies to mitigate any adverse impacts of water quality changes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Anthropogenic and biogenic ligands may mobilize uranium (U) from tetravalent U (U(IV)) phases in the subsurface, especially from labile noncrystalline U(IV). The rate and extent of U(IV) mobilization are affected by geochemical processes. Competing metals and humic substances may play a decisive role in U mobilization by anthropogenic and biogenic ligands. A structurally diverse set of anthropogenic and biogenic ligands was selected for assessing the effect of the aforementioned processes on U mobilization from noncrystalline U(IV), including 2,6-pyridinedicarboxylic acid (DPA), citrate, N , N '-di(2-hydroxybenzyl)ethylene-diamine- N , N '-diacetic acid (HBED), and desferrioxamine B (DFOB). All experiments were performed under anoxic conditions at pH 7.0. The effect of competing metals (Ca, Fe(III), and Zn) on ligand-induced U mobilization depended on the particular metal-ligand combination ranging from nearly complete U mobilization inhibition (e.g., Ca-citrate) to no apparent inhibitory effects or acceleration of U mobilization (e.g., Fe(III)-citrate). Humic substances (Suwannee River humic acid and fulvic acid) were tested across a range of concentrations either separately or combined with the aforementioned ligands. Humic substances alone mobilized appreciable U and also enhanced U mobilization in the presence of anthropogenic or biogenic ligands. These findings illustrate the complex influence of competing metals and humic substances on U mobilization by anthropogenic and biogenic ligands in the environment.

The dynamics of Pb(II) at mineral surfaces affect its mobility in the environment. Pb(II) forms inner- and outer-sphere complexes on mineral surfaces, and this adsorbed pool often represents a large portion of the bioaccessible Pb in contaminated soils. To assess the lability of this potentially reactive adsorbed Pb(II) pool at metal oxide surfaces, we performed Pb(II) isotope exchange measurements between dissolved Pb(II) enriched in 207 Pb and natural isotopic abundance Pb(II) adsorbed to rutile at pH 5, 6, and 7. We find that ∼95% of the adsorbed lead is exchangeable. An initially fast exchange (<1 h) is followed by a slower exchange that occurs on a time scale of hours to days. Pb L III -edge extended X-ray absorption fine structure spectra indicate that similar binding mechanisms are present at all pH values and Pb(II) loadings, implying that differences in exchange rates across the pH range examined are not attributable to changes in the coordination environment. The slower exchange at pH 5 may be associated with interparticle and intraparticle diffusion resulting from particle aggregation. These findings demonstrate that the dissolved Pb(II) pool can be rapidly replenished by adsorbed Pb(II) if this pool is drawn down incrementally by biological uptake or a shift in chemical conditions.

Lead(IV) oxide (PbO 2 ) is one of the lead corrosion products that forms on the inner surface of lead pipes used for drinking water supply. It can maintain low dissolved Pb(II) concentrations when free chlorine is present. When free chlorine is depleted, PbO 2 and soluble Pb(II) will co-occur in these systems. This study used a stable lead isotope ( 207 Pb) as a tracer to examine the interaction between aqueous Pb(II) and solid PbO 2 at conditions with no net change in dissolved Pb concentration. While the dissolved Pb(II) concentration remained unchanged, significant isotope exchange occurred that indicated that substantial amounts (24.3-35.0% based on the homogeneous recrystallization model) of the Pb atoms in the PbO 2 solids had been exchanged with those in solution over 264 h. Neither α-PbO 2 nor β-PbO 2 displayed a change in mineralogy, particle size, or oxidation state after reaction with aqueous Pb(II). The combined isotope exchange and solid characterization results indicate that redox-driven recrystallization of PbO 2 had occurred. Such redox-driven recrystallization is likely to occur in water that stagnates in lead pipes that contain PbO 2 , and this recrystallization may alter the reactivity of PbO 2 with respect to its stability and susceptibility to reductive dissolution.

Microbial reduction of soluble hexavalent uranium (U(VI)) to sparingly soluble tetravalent uranium (U(IV)) has been explored as an in situ strategy to immobilize U. Organic ligands might pose a potential hindrance to the success of such remediation efforts. In the current study, a set of structurally diverse organic ligands were shown to enhance the dissolution of crystalline uraninite (UO 2 ) for a wide range of ligand concentrations under anoxic conditions at pH 7.0. Comparisons were made to ligand-induced U mobilization from noncrystalline U(IV). For both U phases, aqueous U concentrations remained low in the absence of organic ligands (<25 nM for UO 2 ; 300 nM for noncrystalline U(IV)). The tested organic ligands (2,6-pyridinedicarboxylic acid (DPA), desferrioxamine B (DFOB), N , N '-di(2-hydroxybenzyl)ethylene-diamine- N , N '-diacetic acid (HBED), and citrate) enhanced U mobilization to varying extents. Over 45 days, the ligands mobilized only up to 0.3% of the 370 μM UO 2 , while a much larger extent of the 300 μM of biomass-bound noncrystalline U(IV) was mobilized (up to 57%) within only 2 days (>500 times more U mobilization). This work shows the potential of numerous organic ligands present in the environment to mobilize both recalcitrant and labile U forms under anoxic conditions to hazardous levels and, in doing so, undermine the stability of immobilized U(IV) sources.

Phosphate addition is commonly applied as an effective method to remediate lead contaminated sites via formation of low solubility lead phosphate solids. However, subsequent transport of the lead phosphate particles may impact the effectiveness of this remediation strategy. Hence, this study investigates the mechanisms involved in the aggregation of lead phosphate particles and their deposition in sand columns as a function of typical water chemistry parameters. Clean bed filtration theory was evaluated to predict the particle deposition behavior, using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to estimate particle-substrate interactions. The observed particle deposition was not predictable from the primary energy barrier in clean bed filtration models, even in simple monovalent background electrolyte (NaNO 3 ), because weak deposition in a secondary energy minimum prevailed even at low ionic strength, and ripening occurred at ionic strengths of 12.5 mM or higher. For aged (aggregated) suspensions, straining also occurred at 12.5 mM or higher. Aggregation and deposition were further enhanced at low total P/Pb ratios (i.e., P/Pb = 1) and in the presence of divalent cations, such as Ca 2+ (≥ 0.2 mM), which resulted in less negative particle surface potentials and weaker electrostatic repulsion forces. However, the presence of 5 mg C/L of humic acid induced strong steric or electrosteric repulsion, which hindered particle aggregation and deposition even in the presence of Ca 2+ . This study demonstrates the importance of myriad mechanisms in lead phosphate deposition and provides useful information for controlling water chemistry in phosphate applications for lead remediation., (Copyright © 2022. Published by Elsevier Ltd.)

Removing dissolved selenium (i.e., selenate and selenite) from wastewater is a challenging issue for a range of industries. Iron electrocoagulation can produce Fe(II)-containing solids that can adsorb and chemically reduce dissolved Se. In a series of bench-scale experiments we investigated the effects of dissolved oxygen (fully oxic, partially oxic, and strictly anoxic) and pH (6 and 8) on the rate and extent of dissolved selenate and selenite removal by iron electrocoagulation. These studies combined measurements of the aqueous phase with the direct characterization of the resulting solids. Among the conditions studied the rate and extent of dissolved selenium (Se) removal were highest at pH 8 and strictly anoxic conditions. X-ray absorption spectroscopy demonstrated that in the absence of oxygen, Se was primarily transformed to elemental selenium (Se 0 ) and selenide. Green rust that formed in the suspension during electrocoagulation played a key role as a reductant and sorbent of Se. At pH 6 dissolved oxygen did not affect the rates and extents of dissolved Se removal. Under all the conditions studied, dissolved Se removal was more effective with iron electrocoagulation than with the direct addition of pre-synthesized green rust or ferrous hydroxide. The most rapid and substantial dissolved Se removal was achieved by freshly-formed green rust and ferrous hydroxide, which are both Fe(II)-bearing solids. With an improved understanding of the products and mechanisms of the process, iron electrocoagulation can be optimized for removal of Se from wastewater., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Adsorption and subsequent reduction of U(VI) on Fe(II)-bearing clay minerals can control the mobility of uranium in subsurface environments. Clays such as montmorillonite provide substantial amounts of the reactive surface area in many subsurface environments, and montmorillonite-containing materials are used in the storage of spent nuclear fuel. We investigated the extent of reduction of U(VI) by Fe(II)-bearing montmorillonite at different pH values and sodium concentrations using X-ray absorption spectroscopy and chemical extractions. Nearly complete reduction of U(VI) to U(IV) occurred at a low sodium concentration at both pH 3 and 6. At pH 6 and a high sodium concentration, which inhibits U(VI) binding at cation-exchange sites, the extent of U(VI) reduction was only 70%. Surface-bound U(VI) on unreduced montmorillonite was more easily extracted into solution with bicarbonate than surface-bound U(IV) generated by reduction of U(VI) on Fe(II)-bearing montmorillonite. We developed a nonelectrostatic surface complexation model to interpret the equilibrium adsorption of U(IV) on Fe(II)-bearing montmorillonite as a function of pH and sodium concentration. These findings establish the potential importance of structural Fe(II) in low iron content smectites in controlling uranium mobility in subsurface environments.

The stability of RNA in aqueous systems is critical for multiple environmental applications including evaluating the environmental fate of RNA interference pesticides and interpreting viral genetic marker abundance for wastewater-based epidemiology. In addition to biological processes, abiotic reactions may also contribute to RNA loss. In particular, some metals are known to dramatically accelerate rates of RNA hydrolysis under certain conditions (i.e., 37 °C or higher temperatures, 0.15-100 mM metal concentrations). In this study, we investigated the extent to which metals catalyze RNA hydrolysis under environmentally relevant conditions. At ambient temperature, neutral pH, and ∼10 μM metal concentrations, we determined that metals that are stronger Lewis acids (i.e., lead, copper) catalyzed single-stranded (ss)RNA, whereas metals that are weaker Lewis acids (i.e., zinc, nickel) did not. In contrast, double-stranded (ds)RNA resisted hydrolysis by all metals. While lead and copper catalyzed ssRNA hydrolysis at ambient temperature and neutral pH values, other factors such as lowering the solution pH and including inorganic and organic ligands reduced the rates of these reactions. Considering these factors along with sub-micromolar metal concentrations typical of environmental systems, we determined that both ssRNA and dsRNA are unlikely to undergo significant metal-catalyzed hydrolysis in most environmental aqueous systems.

A local preschool installed NSF/ANSI 42 and 53 certified point-of-use (POU) filters in its classroom sinks and drinking fountains to protect children from the possibility of elevated lead (Pb) levels in drinking water. We examined the effects of these filters during flowing water and immediately following stagnation periods on Pb, chlorine, and bacterial concentrations in the field and the laboratory. Before and after typical school stagnation periods, we collected samples from filtered classroom sinks, a filtered drinking fountain and nearby unfiltered sinks for a year. No unfiltered samples exceeded Illinois State limits of 5 µg/L for Pb in pre-K through 5th grade schools. However, following stagnation periods as short as overnight (14.5 h), over half of post-stagnation filtered samples from classroom sinks exceeded 5 µg/L while post-stagnation unfiltered samples remained below 5 µg/L. Laboratory testing showed no significant increases in Pb with stagnation, suggesting that the preschool classrooms may have had Pb-bearing plumbing downstream of the filters which released Pb into the filtered drinking water. The filters effectively removed free chlorine (99% decrease) in both the preschool and laboratory. Installing the filters had the unintended consequence of significantly increasing the bacterial concentrations (as measured by qPCR) in the preschool's drinking water and in laboratory filter effluent. Legionella pneumophila, Pseudomonas aeruginosa, and Mycobacterium spp. were not detected in pre-stagnation unfiltered and post-stagnation filtered samples. These results suggest that the installation of POU filters be considered as one component of an overall strategy to decrease Pb concentrations in school drinking water that holistically considers the premise plumbing system. A 5-minute flush significantly decreased concentrations of Pb and bacteria in filtered sinks. Replacing Pb-bearing plumbing components downstream of a POU filter may also be needed to combat Pb levels in drinking water., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Lead oxide (PbO 2 ) has the lowest solubility with free chlorine among Pb corrosion products, but depletion of free chlorine or a switch from free chlorine to monochloramine can cause its reductive dissolution. We previously reported that Cu(II) and Zn(II) inhibited PbO 2 reductive dissolution within 12 h. Here, we expanded on this work by performing longer duration experiments and further exploring the underlying mechanisms. Between 12 and 48 h, Cu(II) and Zn(II) had no discernible effect on PbO 2 reductive dissolution. From 48 to 192 h, Cu(II) and Zn(II) enhanced PbO 2 reductive dissolution. Dissolved oxygen (DO) concentrations followed the same trends as PbO 2 reductive dissolution, indicating that the DO was produced by PbO 2 reductive dissolution. On the basis of extended X-ray absorption fine structure spectra, we hypothesize that the inhibitory effect of Cu(II) and Zn(II) on PbO 2 reductive dissolution (<12 h) is caused by decreasing abundance of protonated sites on the PbO 2 surface. The enhanced dissolution (>48 h) may be caused by competitive adsorption of Cu(II) and Zn(II) with Pb(II), which could limit the adsorption of Pb(II) onto PbO 2 that could otherwise inhibit reductive dissolution. This study indicates that stagnation time plays a vital role in determining cations' effects on the stability of Pb corrosion products.

Adsorption of uranium onto goethite is an important partitioning process that controls uranium mobility in subsurface environments, for which many different surface complexation models (SCMs) have been developed. While individual models can fit the data for which they are parameterized, many perform poorly when compared with experimental data covering a broader range of conditions. There is an imperative need to quantitatively evaluate the variations in the models and to develop a more robust model that can be used with more confidence across the wide range of conditions. We conducted an intercomparison and refinement of the SCMs based on a metadata analysis. By seeking the globally best fit to a composite dataset with wide ranges of pH, solid/sorbate ratios, and carbonate concentrations, we developed a series of models with different levels of complexity following a systematic roadmap. The goethite-uranyl-carbonate ternary surface complexes were required in every model. For the spectroscopically informed models, a triple-plane model was found to provide the best fit, but the performance of the double-layer model with bidentate goethite-uranyl and goethite-uranyl-carbonate complexes was also comparable. Nevertheless, the models that ignore the bidentate feature of uranyl surface complexation consistently performed poorly. The goodness of fitting for the models that ignore adsorption of carbonate and the charge distributions was not significantly compromised compared with that of their counterparts that considered those. This approach of model development for a large and varied dataset improved our understanding of U(VI)-goethite surface reactions and can lead to a path for generating a single set of reactions and equilibrium constants for including U(VI) adsorption onto goethite in reactive transport models.

Sodium silicate is thought to mitigate lead release via two mechanisms: by increasing pH and by forming a protective silica film. A pilot-scale study using an excavated lead service line (LSL) fed with water from a Great Lakes source was undertaken to: (1) clearly distinguish the pH effect and the silica effect; (2) compare sodium silicate to orthophosphate and pH adjustment; (3) determine the nature of silica accumulation in the pipe scale. The LSL was cut into segments and acclimated with water at pH 7.1. Median dissolved lead was 197 µg/L in the last 8 weeks of acclimation and dropped to 16 µg/L, 54 µg/L, and 85 µg/L following treatment with orthophosphate (dose: 2.6 mg-PO 4 /L, pH: 7.9), pH adjustment (pH: 7.9) and sodium silicate (dose: 20 mg-SiO 2 /L, pH: 7.9), respectively. When silica dose was increased from 20 mg-SiO 2 /L to 25 mg-SiO 2 /L (pH: 8.1), lead release destabilized and increased (median dissolved lead: 141 µg/L) due to formation of colloidal dispersions composed mainly of lead- and aluminum-rich phases as detected by field flow fractionation used with inductively coupled plasma mass spectrometry. Si was present in the scale at a maximum of 2.2 atomic % after 17 weeks of silica dosing at 20 mg- SiO 2 /L. Under the conditions tested, sodium silicate did not offer any benefits for reducing lead release from this LSL other than increasing pH. However, sodium silicate resulted in lower levels of biofilm accumulation on pipe walls, as measured by heterotrophic plate counts, when compared to orthophosphate., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier Ltd.)

The effect of sodium silicate addition on lead release from lead service lines (LSLs) was investigated using laboratory-based pipe loop experiments with LSLs harvested from a water utility that has one of the Great Lakes as its source water. The LSLs were first conditioned with a synthetic water similar to that of Buffalo Water that matched the major water chemistry that the pipes had experienced in the field; the one exception was the absence of dissolved organic carbon in the synthetic water. After conditioning, the LSLs were used in tests with the same synthetic water and with sodium silicate added to the water for half of the LSLs. In one test sodium silicate addition was performed with adjustment of the pH to maintain it at the same value (pH 7.7) as before addition. In this test sodium silicate effectively reduced the dissolved and particulate lead concentrations in the water within six weeks of treatment. Periodic assessments of the corrosion scales in the pipes found that sodium silicate accumulated throughout the scale thickness and gradually decreased the lead release. In the other test the pH was allowed to increase from 7.7 to 8.8 upon addition of 20 mg/L as SiO 2 sodium silicates, and parallel control experiments were performed with the same pH increase made using sodium hydroxide addition. In these tests the lead concentrations decreased in both the silicate-treated and control pipes, and the decreases were not significantly different between the silicate-treated and control pipes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This study explored the ability of orthophosphate addition to limit lead release from lead service lines delivering high pH, low alkalinity water. We built pipe loop reactors with lead pipes harvested from Providence, RI, and we operated them with high pH and low alkalinity water of a composition similar to that in Providence. Orthophosphate addition decreased the release of both dissolved and particulate lead to the water. The most substantial decreases in total lead concentrations occurred after 15 weeks of orthophosphate addition, which was associated with the formation of calcium-lead-phosphorus (Ca-Pb-P) solids as part of the pipe scale. Pre-existing hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2(s) ) in the scale of the lead pipe appeared to promote the formation of a Ca-Pb-P solid similar to phosphohedyphane (Ca 2 Pb 3 (PO 4 ) 3 (Cl,F,OH) (s) ). Continuous orthophosphate addition was also associated with the formation of a calcium phosphate solid with features like those of fluorapatite (Ca 5 (PO 4 ) 3 F (s) ) on the outermost layer of the scale. Through promoting the formation of these new solids within and on top of the scales, orthophosphate addition limited release of dissolved and particulate lead. These results demonstrate the ability of orthophosphate to control lead release at higher pH conditions than those for which it has typically been used. In addition to the formation of phosphate solids, PbO 2(s) , which was not present on the as-received pipes, was formed due to the constant supply of free chlorine in the laboratory-scale experiment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The occurrence of aluminum in scales on lead pipes is common. This study aimed to identify factors that influence Al accumulation on oxidized lead surfaces and to determine whether the presence of Al impacts Pb release from corrosion products to water. Al accumulation and Pb release were monitored both with and without the addition of phosphate as a corrosion inhibitor. Pb coupons with corrosion scales were exposed to chlorinated water for up to 198 days to investigate Al accumulation and Pb release. Al accumulation was facilitated by Pb corrosion products, but its accumulation was inhibited by phosphate addition. During the study period, the formation of Al deposits did not affect Pb release when phosphate was absent. In an Al-free system, the addition of 1.0 mg/L phosphate (as P) lowered the dissolved Pb concentration below 1.0 μg/L. In a system containing 200 μg/L Al, the emergence of phosphate's effect on Pb control was delayed, and the dissolved Pb concentration decreased but stabilized at a higher value (10-12 μg/L) than in the Al-free system. Phosphohedyphane (Ca 2 Pb 3 (PO 4 ) 3 Cl) was formed in all phosphate-containing systems, and PbO 2 was formed independent of phosphate addition. The effect of Al on Pb release was probably related to its influence on the composition and morphology of Pb-containing minerals on coupon surfaces. The laboratory study has unavoidable limitations in its ability to simulate all conditions in real lead service lines, but this study still highlights the importance of considering the influence of Al when designing Pb corrosion control strategies.

Natural organic matter-iron (NOM-Fe) colloids are ubiquitous at anoxic-oxic interfaces of subsurface environments. Fe(II) or NOM can chemically reduce Cr(VI) to Cr(III), and the formation of Cr(III)-NOM-Fe colloids can control the fate and transport of Cr. We explored the formation and transport of Cr(III)-humic acid (HA)-Fe colloids upon reaction of Cr(VI) with HA-Fe(II) colloids over a range of environmentally relevant conditions. Cr(VI) was completely reduced by HA-Fe(II) complexes under anoxic conditions, and the formation of Cr(III)-HA-Fe colloids depended on HA concentration (or molar C/Fe ratio) and redox conditions. No colloids formed at HA concentrations below 3.5 mg C/L (C/Fe ratio below 1.6), but Cr(III)-HA-Fe colloids formed at higher HA concentrations. In column experiments, Cr(III)-HA-Fe(III) colloids formed under oxic conditions were readily transported through sand-packed porous media. Colloidal stability measurements further suggest that Cr(III)-HA-Fe colloids are highly stable and persist for at least 20 days without substantial change in particle size. This stability is attributed to the enrichment of free HA adsorbed on the Cr(III)-HA-Fe colloid surfaces, intensifying the electrostatic and/or steric repulsion interactions between particles. The new insights provided here are important for evaluating the long-term fate and transport of Cr in organic-rich redox transition zones.

The chemical oxidation of dissolved Mn(II) to Mn(III/IV) oxides (MnO x ) can lead to the accumulation of Mn deposits in drinking water distribution systems. However, Mn(II) oxidation by free chlorine is quite slow under mild conditions (e.g., pH 7.7 and 1.0 mg/L Cl 2 ). This study found a significant role for Cu(II) in Mn(II) oxidation under conditions relevant to the supply of chlorinated drinking water. At pH 7.7, dissolved Cu(II) accelerated Mn(II) oxidation more than 10 times with a dose of 20 μg/L. Solid characterization revealed that during Mn(II) oxidation, Cu(II) adsorbed to freshly formed MnO x and produced Mn-Cu mixtures (denoted as MnO x -Cu(II)). An autocatalytic model for the reaction kinetics suggested that the freshly formed MnO x -Cu(II) had a much higher catalytic activity than that of pure MnO x . Solid CuO also catalyzed Mn(II) oxidation, and kinetic modeling indicated that after an initial oxidation of Mn(II) facilitated by the CuO surface, the freshly formed MnO x -Cu(II) on CuO surface played the dominant role in accelerating further Mn(II) oxidation. This study indicates a high potential for the formation of Mn oxides at locations in a drinking water distribution system or in premise plumbing where both Mn(II) and Cu(II) are available. It provides insights into the co-occurrence of other metals with Mn deposits that is frequently observed in distribution systems.

For lead pipes that contain PbO 2(s) as a major component of their scales, a change in the residual disinfectant from free chlorine to monochloramine can destabilize the PbO 2(s) and result in dramatic increases in aqueous lead concentrations. Such a scenario occurred in Washington, D.C., in late 2000. That problem was ultimately addressed by the addition of phosphate as a corrosion inhibitor, but it took several months for lead levels to drop below regulatory values. This study sought to determine whether adding phosphate prior to switching the disinfectant could mitigate lead release. Using synthetic tap water and new lead pipes, we developed a set of lead pipes with scales rich in PbO 2(s) and then studied their response to a change from free chlorine to monochloramine. Total lead concentrations remained below 10 μg/L for pipes that received phosphate prior to and during the switch. In contrast, total lead concentrations increased from less than 5 μg/L to more than 150 μg/L as a result of the disinfectant switch when phosphate was not present. Characterization of the pipe scales demonstrated that plattnerite (β-PbO 2(s) ) was the dominant component of the scale prior to the switch, and that the scale gradually transformed into one containing a lead phosphate solid chemically similar to phosphohedyphane (Ca 2 Pb 3 (PO 4 ) 3 (Cl,F,OH) (s) ) when phosphate was present.

Surface-functionalized magnetic nanoparticles are promising adsorbents due to their large surface areas and ease of separation after contaminant removal. In this work, the affinity of Cr(VI) adsorption to 8 nm surface-functionalized superparamagnetic magnetite nanoparticles was determined for surface coatings with amine (trimethyloctadecylammonium bromide, CTAB) and carboxyl (stearic acid, SA) functional groups. Cr(VI) adsorbed more strongly to the CTAB-coated nanoparticles than to the SA-coated materials due to electrostatic interactions between positively charged CTAB and anionic Cr(VI) species. The adsorption of Cr(VI) by CTAB- and SA-coated nanoparticles increased with decreasing pH (4.5-10), which could be simulated by a surface complexation model. Cr(VI) removal performance by the nanocomposite was evaluated for two realistic drinking water compositions. The co-occurrence of divalent cations (Ca 2+ and Mg 2+ ) and Cr(VI) resulted in decreased Cr(VI) adsorption as particles were destabilized, leading to the aggregation and lower effective surface area, confirming the importance of the overall water composition on the performance of novel engineered nanomaterials for water treatment applications.

Dissolved Mn(III) species have recently been recognized as a significant form of Mn in redox transition zones, but their speciation, stability, and reactivity are poorly understood. Besides acting as the intermediate for Mn redox chemistry, Mn(III) can undergo disproportionation producing insoluble Mn oxides and aqueous Mn(II). Using pyrophosphate(PP) as a model ligand, we evaluated the thermodynamic and kinetic stability of Mn(III) complexes. They were stable at circumneutral pH and were prone to (partial) disproportionation at acidic or basic pH. With an initial lag phase, the kinetics of Mn(III)-PP disproportionation was autocatalytic with the produced Mn oxides promoting the disproportionation. X-ray diffraction and the average Mn oxidation state indicated that the solid products were not pure Mn(IV) oxides but a mixture of triclinic birnessite and δ-MnO 2 . Addition of synthetic analogs of the precipitates eliminated the lag phase, confirming their catalytic roles. Thermodynamic calculations adequately predicted the stability regime of Mn(III)-PP. The present results refined the constant for Mn(PP) 2 5- formation, which allows a consistent and quantitative prediction of equilibrium speciation of Mn(III)-Mn(II)-birnessite with PP. A simple and robust model, which incorporated the thermodynamic constraints, autocatalytic rate law, and verified reaction stoichiometry, successfully simulated all kinetic data.

This study aimed to characterize metal contaminant concentrations and assess temporal and spatial variability in the main drinking water sources of Cap-Haïtien, Haiti. Water sources from five communities were sampled in two seasons, June (2014) and October (2014), and analysed for a suite of metals. A geographic information system was used to examine the spatial distribution of sampling points. Metal concentrations were below the US Environmental Protection Agency (USEPA) primary drinking water standards. Mean manganese concentrations were comparatively higher in wells (254.5 µg/L), exceeding the USEPA secondary drinking water standard (50 µg/L). Higher mean Mg/Ca and Ba/Ca ratios (range 2.3-3.4) may indicate different interactions between seawater and groundwater throughout the year. Although metal concentrations were within the limits of the USEPA drinking water standards, emerging contaminants, such as manganese, showed concentrations in excess of recommended limits. These metals may interact with background nutritional status with potential implications for growth and development.

Phosphate is commonly added to drinking water to inhibit lead release from lead service lines and lead-containing materials in premise plumbing. Phosphate addition promotes the formation of lead phosphate particles, and their aggregation behaviors may affect their transport in pipes. Here, lead phosphate formation and aggregation were studied under varied aqueous conditions typical of water supply systems. Under high aqueous PO 4 /Pb molar ratios (>1), phosphate adsorption made the particles more negatively charged. Therefore, enhanced stability of lead phosphate particles was observed, suggesting that although addition of excess phosphate can lower the dissolved lead concentrations in tap water, it may increase concentrations of particulate lead. Adsorption of divalent cations (Ca 2+ and Mg 2+ ) onto lead phosphate particles neutralized their negative surface charges and promoted their aggregation at pH 7, indicating that phosphate addition for lead immobilization may be more efficient in harder waters. The presence of natural organic matter (NOM, ≥ 0.05 mg C/L humic acid and ≥ 0.5 mg C/L fulvic acid) retarded particle aggregation at pH 7. Consequently, removal of organic carbon during water treatment to lower the formation of disinfection-byproducts (DBPs) may have the additional benefit of minimizing the mobility of lead-containing particles. This study provided insight into fundamental mechanisms controlling lead phosphate aggregation. Such understanding is helpful to understand the observed trends of total lead in water after phosphate addition in both field and pilot-scale lead pipe studies. Also, it can help optimize lead immobilization by better controlling the water chemistry during phosphate addition.

Recent laboratory and field studies have demonstrated that basalt formations may present one of the most secure repositories for anthropogenic CO 2 emissions through carbon mineralization. In this work, a series of high-temperature, high-pressure core flooding experiments was conducted to investigate how transport limitations, reservoir temperature, and brine chemistry impact carbonation reactions following injection of CO 2 -rich aqueous fluids into fractured basalts. At 100 °C and 6.3 mM [NaHCO 3 ], representative of typical reservoir conditions, carbonate precipitates were highly localized on reactive mineral grains contributing key divalent cations. Geochemical gradients promoted localized reaction fronts of secondary precipitates that were consistent with 2D reactive transport model predictions. Increasing [NaHCO 3 ] to 640 mM dramatically enhanced carbonation in diffusion-limited zones, but an associated increase in clays filling advection-controlled flow paths could ultimately obstruct flow and limit sequestration capacity under such conditions. Carbonate and clay precipitation were further enhanced at 150 °C, reducing the pre-reaction fracture volume by 48% compared to 35% at 100 °C. Higher temperature also produced more carbonate-driven fracture bridging, which generally increased with diffusion distance into dead-end fractures. In combination, the results are consistent with field tests indicating that mineralization will predominate in buffered diffusion-limited zones adjacent to bulk flow paths and that alkaline reservoirs with strong geothermal gradients will enhance the extent of carbon trapping.

The reaction of manganese oxides with Cr(III)-bearing solids in soils and sediments can lead to the natural production of Cr(VI) in groundwater. Building on previous knowledge of MnO 2 as an oxidant for Cr(III)-containing solids, this study systematically evaluated the rates and mechanisms of the oxidation of Cr(III) in iron oxides by δ-MnO 2 . The Fe/Cr ratio (x = 0.055-0.23 in Cr x Fe 1-x (OH) 3 ) and pH (5-9) greatly influenced the Cr(VI) production rates by controlling the solubility of Cr(III) in iron oxides. We established a quantitative relationship between Cr(VI) production rates and Cr(III) solubility of Cr x Fe 1-x (OH) 3 , which can help predict Cr(VI) production rates at different conditions. The adsorption of Cr(VI) and Mn(II) on solids shows a typical pH dependence for anions and cations. A multichamber reactor was used to assess the role of solid-solid contact in Cr x Fe 1-x (OH) 3 -MnO 2 interactions, which eliminates the contact of the two solids while still allowing aqueous species transport across a permeable membrane. Cr(VI) production rates were much lower in multichamber than in completely mixed batch experiments, indicating that the redox interaction is accelerated by mixing of the solids. Our results suggest that soluble Cr(III) released from Cr x Fe 1-x (OH) 3 solids to aqueous solution can migrate to MnO 2 surfaces where it is oxidized.

The important role of natural organic matter (NOM)-Fe colloids in influencing contaminant transport, and this role can be influenced by the formation, aggregation, and particle deposition dynamics of NOM-Fe colloids. In this work, NOM-Fe colloids at different C/Fe ratios were prepared by mixing different concentrations of humic acid (HA) with 10 mg/L Fe(II) under anoxic conditions. The colloids were characterized by an array of techniques and their aggregation and deposition behaviors were examined under both anoxic and oxic conditions. The colloids are composed of HA-Fe(II) at anoxic conditions, while they are made up of HA-Fe(III) at oxic conditions until the C/Fe molar ratio exceeds 1.6. For C/Fe molar ratios above 1.6, the aggregation and deposition kinetics of HA-Fe(II) colloids under anoxic conditions are slower than those of HA-Fe(III) colloids under oxic conditions. Further, the aggregation of HA-Fe colloids under both anoxic and oxic conditions decreases with increasing C/Fe molar ratio from 1.6 to 23.3. This study highlights the importance of the redox transformation of Fe(II) to Fe(III) and the C/Fe ratio for the formation and stability of NOM-Fe colloids that occur in subsurface environments with anoxic-oxic interfaces.

Surface-functionalized magnetite nanoparticles have high capacity for U(VI) adsorption and can be easily separated from the aqueous phase by applying a magnetic field. A surface-engineered bilayer structure enables the stabilization of nanoparticles in aqueous solution. Functional groups in stearic acid (SA), oleic acid (OA), and octadecylphosphonic acid (ODP) coatings led to different adsorption extents (SA≈ OA > ODP) under the same conditions. The impact of water chemistry (initial loading of U(VI), pH, and the presence of carbonate) has been systematically examined for U(VI) adsorption to OA-coated nanoparticles. A diffuse double layer surface complexation model was developed for surface-functionalized magnetite nanoparticles that could simulate both the measured surface charge and the U(VI) adsorption behavior at the same time. With a small set of adsorption reactions for uranyl hydroxide and uranyl carbonate complexes to surface sites, the model can successfully simulate the entire adsorption data set over all uranium loadings, pH values, and dissolved inorganic carbon concentrations. The results show that the adsorption behavior was related to the changing U(VI) species and properties of surface coatings on nanoparticles. The model could also fit pH-dependent surface potential values that are consistent with measured zeta potentials.

Basalt formations could enable secure long-term carbon storage by trapping injected CO 2 as stable carbonates. Here, a predictive modeling framework was designed to evaluate the roles of transport limitations and mineral spatial distributions on mineral dissolution and carbonation reactions in fractured basalts exposed to CO 2 -acidified fluids. Reactive transport models were developed in CrunchTope based on data from high-temperature, high-pressure flow-through experiments. Models isolating the effect of transport compared nine flow conditions under the same mineralogy. Heterogeneities were incorporated by segmenting an actual reacted basalt sample, and these results were compared to equivalent flow conditions through randomly generated mineral distributions with the same bulk composition. While pure advective flow with shorter retention times promotes rapid initial carbonation, pure diffusion sustains mineral reactions for longer time frames and generates greater net carbonate volumes. For the same transport conditions and bulk composition, exact mineral spatial distributions do not impact the amount of carbonation but could determine the location by controlling local solution saturation with respect to secondary carbonates. In combination, the results indicate that bulk mineralogy will be more significant than small-scale heterogeneities in controlling the rate and extent of CO 2 mineralization, which will likely occur in diffusive zones adjacent to flow paths or in dead-end fractures.

Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1-200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.

Fractures and pores in basalt could provide substantial pore volume and surface area of reactive minerals for carbonate mineral formation in geologic carbon sequestration. In many fractures solute transport will be limited to diffusion, and opposing chemical gradients that form as a result of concentration differences can lead to spatial distribution of silicate mineral dissolution and carbonate mineral precipitation. Glass tubes packed with grains of olivine or basalt with different grain sizes and compositions were used to explore the identity and spatial distribution of carbonate minerals that form in dead-end one-dimensional diffusion-limited zones that are connected to a larger reservoir of water in equilibrium with 100 bar CO 2 at 100 °C. Magnesite formed in experiments with olivine, and Mg- and Ca-bearing siderite formed in experiments with flood basalt. The spatial distribution of carbonates varied between powder packed beds with different powder sizes. Packed beds of basalt powder with large specific surface areas sequestered more carbon per unit basalt mass than powder with low surface area. The spatial location and extent of carbonate mineral formation can influence the overall ability of fractured basalt to sequester carbon.

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred only at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.

The potential for new U.S. regulations for Cr(VI) in drinking water have spurred strong interests in improving technologies for Cr(VI) removal. This study examined iron electrocoagulation for Cr(VI) removal at conditions directly relevant to drinking water treatment. Cr(VI) is chemically reduced to less soluble Cr(III) species by the Fe(II) produced from an iron anode, and XANES spectra indicate that the Cr is entirely Cr(III) in solid-phases produced in electrocoagulation. The dynamics of Cr(VI) removal in electrocoagulation at pH 6 and pH 8 at both oxic and anoxic conditions can be described by a new model that incorporates Fe(II) release from the anode and heterogeneous and homogeneous reduction of Cr(VI) by Fe(II). Heterogeneous Cr(VI) reduction by adsorbed Fe(II) was critical to interpreting Cr(VI) removal at pH 6, and the Fe- and Cr-containing EC product was found to catalyze the redox reaction. Dissolved oxygen (DO) did not observably inhibit Cr(VI) removal because Fe(II) reacts with DO more slowly than it does with Cr(VI), and Cr(VI) removal was faster at higher pH. Even in the presence of common groundwater solutes, iron electrocoagulation lowered Cr(VI) concentrations to levels well below California's 10 μg/L.

Determination of equilibrium constants describing chemical reactions in the aqueous phase and at solid-water interface relies on inverse modeling and parameter estimation. Although there are existing tools available, the steep learning curve prevents the wider community of environmental engineers and chemists to adopt those tools. Stemming from classical chemical equilibrium codes, MINEQL+ has been one of the most widely used chemical equilibrium software programs. We developed a spreadsheet-based tool, which we are calling MINFIT, that interacts with MINEQL+ to perform parameter estimations that optimize model fits to experimental data sets. MINFIT enables automatic and convenient screening of a large number of parameter sets toward the optimal solutions by calling MINEQL+ to perform iterative forward calculations following either exhaustive equidistant grid search or randomized search algorithms. The combined use of the two algorithms can securely guide the searches for the global optima. We developed interactive interfaces so that the optimization processes are transparent. Benchmark examples including both aqueous and surface complexation problems illustrate the parameter estimation and associated sensitivity analysis. MINFIT is accessible at http://minfit.strikingly.com .

Organisms have developed different strategies to cope with environmental conditions of low Fe availability based on the exudation of reducing, ligating, and acidifying compounds. In the context of Fe acquisition from soil, the effects of these reactive compounds have generally been considered independent and additive. However, highly efficient Fe acquisition strategies may rely on synergistic effects between reactive exudates. In the present study, we demonstrate that synergistic effects between biogenic ligands and a reductant (ascorbate) can occur in Fe mobilization from soil. Synergistic Fe mobilization was found for all ligands examined (desferrioxamine B (DFOB), 2'-deoxymugineic acid (DMA), esculetin, and citrate). The size and duration of the synergistic effect on Fe mobilization varied with ligand: larger effects were observed for the sideorphores compared to esculetin and citrate. For DFOB, the synergistic effect lasted for the 168 h duration of the experiment; for DMA, an initial synergistic effect turned into an antagonistic effect after 4 h because of enhanced mobilization of competing metals; and for esculetin and citrate, the synergistic effect was temporary (less than 24 h). Our results demonstrate that synergistic effects greatly enhance the reactivity of mixtures of compounds known to be exuded in response to Fe limitation. These synergistic effects could be decisive for the survival of plants and microorganisms under conditions of low Fe availability.

Waters that return to the surface after injection of a hydraulic fracturing fluid for gas and oil production contain elements, including regulated metals and metalloids, which are mobilized through interactions between the fracturing fluid and the shale formation. The rate and extent of mobilization depends on the geochemistry of the formation and the chemical characteristics of the fracturing fluid. In this work, laboratory scale experiments investigated the influence of water chemistry on element mobilization from core samples taken from the Bakken formation, one of the most productive shale oil plays in the US. Fluid properties were systematically varied and evaluated with regard to pH, oxidant level, solid:water ratio, temperature, and chemical additives. Element mobilization strongly depended on solution pH and redox conditions and to a lesser extent on the temperature and solid:water ratio. The presence of oxygen and addition of hydrogen peroxide or ammonium persulfate led to pyrite oxidation, resulting in elevated sulfate concentrations. Further, depending on the mineral carbonates available to buffer the system pH, pyrite oxidation could lower the system pH and enhance the mobility of several metals and metalloids., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Phosphate addition to subsurface environments contaminated with uranium can be used as an in situ remediation approach. Batch experiments were conducted to evaluate the dependence of the extent and mechanism of uranium uptake on the pathway for reaction with calcium phosphates. At pH 4.0 and 6.0 uranium uptake from solution occurred via autunite (Ca(UO2)2(PO4)2) precipitation irrespective of the starting forms of calcium and phosphate. At pH 7.5, a condition at which calcium phosphate solids could form, the uptake mechanism depended on the nature of the calcium and phosphate as determined by X-ray absorption spectroscopy and laser-induced fluorescence spectroscopy. When dissolved uranium, calcium, and phosphate were added simultaneously, uranium was structurally incorporated into a newly formed amorphous calcium phosphate solid. Adsorption was the dominant removal mechanism for uranium contacted with preformed amorphous calcium phosphate solids. When U(VI) was added to a suspension containing amorphous calcium phosphate solids as well as dissolved calcium and phosphate, then removal occurred through precipitation (57 ± 4%) of autunite and adsorption (43 ± 4%) onto calcium phosphate. Dissolved uranium, calcium, and phosphate concentrations with saturation index calculations helped identify removal mechanisms and determine thermodynamically favorable solid phases.

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

The adsorption of arsenic to iron oxyhydroxides strongly depends on water chemistry. Iron(III) oxyhydroxides can also participate in the oxidation of As(III) to As(V), which changes arsenic's toxicity and adsorption behavior. As(III) and As(V) adsorption to lepidocrocite (γ-FeOOH) were examined in batch experiments that explored the effects of lepidocrocite dose, pH, availability of dissolved oxygen, and the presence of aqueous Fe(II) on adsorption. Lepidocrocite is an iron oxyhydroxide found in soils, and it is one of the major products of iron electrocoagulation for water treatment. A surface complexation model was able to describe the adsorption of both As(III) and As(V) to lepidocrocite over a broad range of conditions. The concentration and oxidation states of arsenic in solution were measured over the course of the reactions. At both oxic and anoxic conditions, As(III) was oxidized to As(V) in systems that contained lepidocrocite together with Fe(II); this oxidation led to overall enhanced arsenic adsorption at near neutral pH. With oxygen the pH-dependent generation of oxidants from the Fenton reaction drove the As(III) oxidation. In the absence of oxygen the As(III) was probably oxidized by Fe(III) in lepidocrocite that had become more reactive upon reaction with Fe(II)., (Copyright © 2015 Elsevier Inc. All rights reserved.)

We have developed an approach for determining pH at elevated pressures and temperatures by using (13)C NMR measurements of inorganic carbon species together with a geochemical equilibrium model. The approach can determine in situ pH with precision better than 0.1 pH units at pressures, temperatures, and ionic strengths typical of geologic carbon sequestration systems. A custom-built high pressure NMR probe was used to collect (13)C NMR spectra of (13)C-labeled CO2 reactions with NaOH solutions and Mg(OH)2 suspensions at pressures up to 107 bar and temperatures of 80 °C. The quantitative nature of NMR spectroscopy allows the concentration ratio [CO2]/[HCO3(-)] to be experimentally determined. This ratio is then used with equilibrium constants calculated for the specific pressure and temperature conditions and appropriate activity coefficients for the solutes to calculate the in situ pH. The experimentally determined [CO2]/[HCO3(-)] ratios agree well with the predicted values for experiments performed with three different concentrations of NaOH and equilibration with multiple pressures of CO2. The approach was then applied to experiments with Mg(OH)2 slurries in which the change in pH could track the dissolution of CO2 into solution, rapid initial Mg(OH)2 dissolution, and onset of magnesium carbonate precipitation.

Phosphate amendments can be added to U(VI)-contaminated subsurface environments to promote in situ remediation. The primary objective of this study was to evaluate the impacts of phosphate addition on the transport of U(VI) through contaminated sediments. In batch experiments using sediments (<2 mm size fraction) from a site in Rifle, Colorado, U(VI) only weakly adsorbed due to the dominance of the aqueous speciation by Ca-U(VI)-carbonate complexes. Column experiments with these sediments were performed with flow rates that correspond to a groundwater velocity of 1.1 m/day. In the absence of phosphate, the sediments took up 1.68-1.98 μg U/g of sediments when the synthetic groundwater influent contained 4 μM U(VI). When U(VI)-free influents were then introduced with and without phosphate, substantially more uranium was retained within the column when phosphate was present in the influent. Sequential extractions of sediments from the columns revealed that uranium was uniformly distributed along the length of the columns and was primarily in forms that could be extracted by ion exchange and contact with a weak acid. Laser induced fluorescence spectroscopy (LIFS) analysis along with sequential extraction results suggest adsorption as the dominant uranium uptake mechanism. The response of dissolved uranium concentrations to stopped-flow events and the comparison of experimental data with simulations from a simple reactive transport model indicated that uranium adsorption to and desorption from the sediments was not always at local equilibrium., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Groundwater composition and coupled redox cycles can affect the long-term stability of U(IV) products from bioremediation. The effects of Mn(II), a redox active cation present at uranium-contaminated sites, on UO2 dissolution in both oxic and anoxic systems were investigated using batch and continuous-flow reactors. Under anoxic conditions Mn(II) inhibited UO2 dissolution, which was probably due to adsorption of Mn(II) and precipitation of MnCO3 that decreased exposure of U(IV) surface sites to oxidants. In contrast, Mn(II) promoted UO2 dissolution under oxic conditions through Mn redox cycling. Oxidation of Mn(II) by O2 produced reactive Mn species, possibly short-lived Mn(III) in solution or at the surface, that oxidatively dissolved the UO2 more rapidly than could the O2 alone. At pH 8 the Mn cycling was such that there was no measurable accumulation of particulate Mn oxides. At pH 9 Mn oxides could be produced and accumulate, while they were continuously reduced by UO2, with Mn(II) returning to the aqueous phase. With the rapid turnover of Mn in the redox cycle, concentrations of Mn as low as 10 μM could maintain an enhanced UO2 dissolution rate. The presence of the siderophore desferrioxamine B (a strong Mn(III)-complexing ligand) effectively decoupled the redox interactions of uranium and manganese to suppress the promotional effect of Mn(II).

Hydrocerussite (Pb3(CO3)2(OH)2) is widely observed as a corrosion product in drinking water distribution systems. Its equilibrium solubility and dissolution rate can control lead concentrations in drinking water. The dissolution rate of hydrocerussite was investigated as a function of pH, dissolved inorganic carbon (DIC), and orthophosphate concentrations at conditions relevant to drinking water distribution using continuously stirred tank reactors (CSTRs). In the absence of DIC and orthophosphate, the dissolution rate decreased with increasing pH. Addition of DIC inhibited the dissolution of hydrocerussite. The addition of orthophosphate significantly decreased the dissolution rate of hydrocerussite. At conditions with orthophosphate and without DIC, a lead(II) phosphate solid hydroxylpyromorphite (Pb5(PO4)3OH) was observed after reaction, and orthophosphate's inhibitory effect can be attributed to the formation of this low-solubility lead(II) phosphate solid. In the presence of both orthophosphate and DIC, no lead(II) phosphate solid was observed, but the rate was still lowered by the presence of orthophosphate, which might be due to the adsorption of orthophosphate to block reactive sites on the hydrocerussite surface. For systems in which hydroxylpyromorphite was present, the steady-state effluent lead concentrations from the CSTRs were close to the predicted equilibrium solubility of hydroxylpyromorphite. In the absence of orthophosphate rapid equilibration of hydrocerussite was observed., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The stability of UO2 is critical to the success of reductive bioremediation of uranium. When reducing conditions are no longer maintained, Mn redox cycling may catalytically mediate the oxidation of UO2 and remobilization of uranium. Ligand-stabilized soluble Mn(III) was recently recognized as an important redox-active intermediate in Mn biogeochemical cycling. This study evaluated the kinetics of oxidative UO2 dissolution by soluble Mn(III) stabilized by pyrophosphate (PP) and desferrioxamine B (DFOB). The Mn(III)-PP complex was a potent oxidant that induced rapid UO2 dissolution at a rate higher than that by a comparable concentration of dissolved O2. However, the Mn(III)-DFOB complex was not able to induce oxidative dissolution of UO2. The ability of Mn(III) complexes to oxidize UO2 was probably determined by whether the coordination of Mn(III) with ligands allowed the attachment of the complexes to the UO2 surface to facilitate electron transfer. Systematic investigation into the kinetics of UO2 oxidative dissolution by the Mn(III)-PP complex suggested that Mn(III) could directly oxidize UO2 without involving particulate Mn species (e.g., MnO2). The expected 2:1 reaction stoichiometry between Mn(III) and UO2 was observed. The reactivity of soluble Mn(III) in oxidizing UO2 was higher at lower ratios of pyrophosphate to Mn(III) and lower pH, which is probably related to differences in the ligand-to-metal ratio and/or protonation states of the Mn(III)-pyrophosphate complexes. Disproportionation of Mn(III)-PP occurred at pH 9.0, and the oxidation of UO2 was then driven by both MnO2 and soluble Mn(III). Kinetic models were derived that provided excellent fits of the experimental results.