Modeling the Role in pH on Contaminant Sequestration by Zerovalent Metals: Chromate Reduction by Zerovalent Magnesium.

The role of pH in sequestration of Cr(VI) by zerovalent magnesium (ZVMg) was characterized by global fitting of a kinetic model to time-series data from unbuffered batch experiments with varying initial pH values. At initial pH values ranging from 2.0 to 6.8, ZVMg (0.5 g/L) completely reduced Cr(VI) (18.1 µM) within 24 h, during which time pH rapidly increased to a plateau value of ∼10. Time-series correlation analysis of the pH and aqueous Cr(VI), Cr(III), and Mg(II) concentration data suggested that these conditions are controlled by combinations of reactions (involving Mg0 oxidative dissolution and Cr(VI) sequestration) that evolve over the time course of each experiment. Since this is also likely to occur during any engineering applications of ZVMg for remediation, we developed a kinetic model for dynamic pH changes coupled with ZVMg corrosion processes. Using this model, the synchronous changes in Cr(VI) and Mg(II) concentrations were fully predicted based on the Langmuir-Hinshelwood kinetics and transition-state theory, respectively. The reactivity of ZVMg was different in two pH regimes that were pH-dependent at pH < 4 and pH-independent at the higher pH. This contrasting pH effect could be ascribed to the shift of the primary oxidant of ZVMg from H+ to H2O at the lower and higher pH regimes, respectively.

Rhodochrosite Oxidation by Dissolved Oxygen and the Formation of Mn Oxide Product: The Impact of Goethite as a Foreign Solid Substrate.

Rhodochrosite conversion to Mn (oxyhydr)oxides significantly affects the fate and transport of various substances in the environment. We examined rhodochrosite oxidation by dissolved oxygen and the oxidation product formation with an emphasis on the effects of goethite substrate. Without goethite, rhodochrosite oxidation was slow as no detectable change was observed for 28 d with microscopic and spectroscopic analyses, except a minor change in X-ray diffraction. Interestingly, by contrast, it was greatly accelerated and completed in 7 d in the presence of goethite, resulting in the heteroepitaxial growth of groutite (α-MnOOH)-like Mn oxides on the goethite (α-FeOOH) tip surfaces. The formation of this secondary Mn oxide likely induced the acidification of the microenvironment in the vicinity of rhodochrosite particles and thereby promoted their dissolution. Subsequently, their oxidative conversion to the Mn oxide was expedited by the surface catalyzed Mn(II) oxidation on the goethite tip. Our results revealed that goethite as a foreign substrate imparts a decisive control on not only the rate but also the type of the reaction product of rhodochrosite oxidation. This study presents a new insight into the geochemical roles of foreign particles on the dynamics of redox-sensitive solid phases in the environment.

Cr(VI) Formation via Oxyhalide-Induced Oxidative Dissolution of Chromium Oxide/Hydroxide in Aqueous and Frozen Solution.

The oxidative dissolution of Cr(III) species (Cr2O3 and Cr(OH)3) by oxyhalide species, which produces hexavalent chromium (Cr(VI)), was studied in aqueous and frozen solution. The oxyhalide-induced oxidation of Cr(III) in frozen solution showed a different trend from that in aqueous solution. Cr(VI) production was higher in frozen than aqueous solution with hypochlorous acid (HOCl) and bromate (BrO3-) but suppressed in frozen solution with hypobromous acid (HOBr) and periodate (IO4-). In particular, bromate markedly enhanced Cr(VI) production in frozen solution, whereas it had a negligible activity in aqueous solution. On the contrary, periodate produced Cr(VI) significantly in aqueous solution but greatly suppressed it in frozen solution. Bromate was found to be much more concentrated in the ice grain boundary than periodate according to both chemical and Raman spectral analyses. The oxidative transformation of Cr(III) to Cr(VI) was accompanied by the concurrent and stoichiometric reduction of oxyhalide species. Dissolved O2 had little effect on the oxidative dissolution, but dissolved organic matter retarded the oxidation of Cr2O3 in both aqueous and frozen conditions. This study proposes that the oxyhalide-induced oxidation of Cr(III) (particularly by bromate) in frozen conditions might have a significant effect on the generation of Cr(VI) in the frozen environment.

Correction to: Potential CO2 intrusion in near-surface environments: a review of current research approaches to geochemical processes.

In the original publication of the article, the third author name has been misspelt. The correct name is given in this correction. The original version of this article was revised.

Stability of Sn-Pd-Kaolinite catalyst during heat treatment and nitrate reduction in continuous flow reaction.

In this study, a novel and highly reactive Sn-Pd catalyst supported by environmentally benign kaolinite (Sn-Pd-kaolinite) was developed and evaluated for stability for effective nitrate (NO3-) reduction in batch and continuous mode. Complete NO3- removal with fast reduction kinetics (k = 18.16 × 10-2 min-1) and 71% selectivity toward N2 were achieved by the Sn-Pd-kaolinite catalyst during batch reactions. During continuous tests, 100% NO3- removal and 80% N2 was achieved for 60 h. However, NO3- removal efficiency gradually decreased to 80% in170 h. The catalyst was then successfully regenerated in the system by increasing H2 flow which achieved a complete NO3- removal again. The metal leaching from catalyst surface was negligible (Sn 0.01% and Pd 0.006%) and the structure was stable during the continuous test, confirming that the Sn-Pd-Kaolinite catalyst had a superior reaction kinetics and operational durability.

Potential CO2 intrusion in near-surface environments: a review of current research approaches to geochemical processes.

Carbon dioxide (CO2) capture and storage (CCS) plays a crucial role in reducing carbon emissions to the atmosphere. However, gas leakage from deep storage reservoirs, which may flow back into near-surface and eventually to the atmosphere, is a major concern associated with this technology. Despite an increase in research focusing on potential CO2 leakage into deep surface features and aquifers, a significant knowledge gap remains in the geochemical changes associated with near-surface. This study reviews the geochemical processes related to the intrusion of CO2 into near-surface environments with an emphasis on metal mobilization and discusses about the geochemical research approaches, recent findings, and current knowledge gaps. It is found that the intrusion of CO2(g) into near-surface likely induces changes in pH, dissolution of minerals, and potential degradation of surrounding environments. The development of adequate geochemical research approaches for assessing CO2 leakage in near-surface environments, using field studies, laboratory experiments, and/or geochemical modeling combined with isotopic tracers, has promoted extensive surveys of CO2-induced reactions. However, addressing knowledge gaps in geochemical changes in near-surface environments is fundamental to advance current knowledge on how CO2 leaks from storage sites and the consequences of this process on soil and water chemistry. For reliable detection and risk management of the potential impact of CO2 leakage from storage sites on the environmental chemistry, currently available geochemical research approaches should be either combined or used independently (albeit in a manner complementarily to one another), and the results should be jointly interpreted.

Defluoridation of water by Tea-bag model using La(3+) modified synthetic resin@chitosan biocomposite.

The aim of this work is to gain a better understanding of the formation of lanthanum complex onto iminodiacetic acid and chitosan (CS@La-IDAMP) composite for effective removal of fluoride from aqueous solution using a tea-bag model for the first time. The surface textural and chemical properties of the synthesized composites were characterized by FTIR, SEM with EDAX and mapping images. The experimental data revealed that the fluoride adsorption was rapid, maximum fluoride removal could be removed within 12min contact time at neutral pH in room temperature under batch equilibrium model. The equilibrium data for adsorption of fluoride on the synthesized blends were well represented by the Freundlich isotherm, giving a maximum adsorption capacity of 17.50mg/g. The adsorption kinetic models were also examined and it was found that all the sorption processes were better described by the pseudo-second-order model. This results suggested that the efficiency of the fluoride removal process was mainly controlled by electrostatic attraction and ion-exchange mechanism. Furthermore, the CS@La-IDAMP material was tested for the regeneration ability with the suitable regenerant to make this process as cost-effective. Finally, it can be concluded that the composite material is the potential adsorbent for the treatment of fluoride from water.

Geochemical characteristics and microbial community composition in toxic metal-rich sediments contaminated with Au-Ag mine tailings.

The effects of extreme geochemical conditions on microbial community composition were investigated for two distinct sets of sediment samples collected near weathered mine tailings. One set (SCH) showed extraordinary geochemical characteristics: As (6.7-11.5%), Pb (1.5-2.1%), Zn (0.1-0.2%), and pH (3.1-3.5). The other set (SCL) had As (0.3-1.2%), Pb (0.02-0.22%), and Zn (0.01-0.02%) at pH 2.5-3.1. The bacterial communities in SCL were clearly different from those in SCH, suggesting that extreme geochemical conditions affected microbial community distribution even on a small spatial scale. The clones identified in SCL were closely related to acidophilic bacteria in the taxa Acidobacterium (18%), Acidomicrobineae (14%), and Leptospirillum (10%). Most clones in SCH were closely related to Methylobacterium (79%) and Ralstonia (19%), both well-known metal-resistant bacteria. Although total As was extremely high, over 95% was in the form of scorodite (FeAsO4·2H2O). Acid-extractable As was only ∼118 and ∼14 mg kg(-1) in SCH and SCL, respectively, below the level known to be toxic to bacteria. Meanwhile, acid-extractable Pb and Zn in SCH were above toxic concentrations. Because As was present in an oxidized, stable form, release of Pb and/or Zn (or a combination of toxic metals in the sediment) from the sediment likely accounts for the differences in microbial community structure. The results also suggest that care should be taken when investigating mine tailings, because large differences in chemical/biological properties can occur over small spatial scales.

Cr(OH)3(s) oxidation induced by surface catalyzed Mn(II) oxidation.

We examined the feasibility of Cr(OH)3(s) oxidation mediated by surface catalyzed Mn(II) oxidation under common groundwater pH conditions as a potential pathway of natural Cr(VI) contaminations. Dissolved Mn(II) (50 µM) was reacted with or without synthesized Cr(OH)3(s) (1.0 g/L) at pH 7.0-9.0 under oxic or anoxic conditions. Homogeneous Mn(II) oxidation by dissolved O2 was not observed at pH ≤ 8.0 for 50 days. At pH 9.0, by contrast, dissolved Mn(II) was completely removed within 8 days and precipitated as hausmannite. When Cr(OH)3(s) was present, this solid was oxidized and released substantial amounts of Cr(VI) as dissolved Mn(II) was added into the suspension at pH ≥ 8.0 under oxic conditions. Production of Cr(VI) was attributed to Cr(OH)3(s) oxidation by a newly formed Mn oxide via Mn(II) oxidation catalyzed on Cr(OH)3(s) surface. XANES results indicated that this surface-catalyzed Mn(II) oxidation produced a mixed valence Mn(III/IV) solid phase. Our results suggest that toxic Cr(VI) can be naturally produced via Cr(OH)3(s) oxidation coupled with the oxidation of dissolved Mn(II). In addition, this study evokes the potential environmental hazard of sparingly soluble Cr(OH)3(s), which has been considered the most common and a stable remediation product of Cr(VI) contamination.

Geochemical implications of gas leakage associated with geologic CO2 storage--a qualitative review.

Gas leakage from deep storage reservoirs is a major risk factor associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers and the vadose zone is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. This paper reviews the current literature and discusses current knowledge gaps on how elevated CO(2) levels could influence geochemical processes (e.g., adsorption/desorption and dissolution/precipitation) in potable aquifers and the vadose zone. The review revealed that despite an increase in research and evidence for both beneficial and deleterious consequences of CO(2) migration into potable aquifers and the vadose zone, significant knowledge gaps still exist. Primary among these knowledge gaps is the role/influence of pertinent geochemical factors such as redox condition, CO(2) influx rate, gas stream composition, microbial activity, and mineralogy in CO(2)-induced reactions. Although these factors by no means represent an exhaustive list of knowledge gaps we believe that addressing them is pivotal in advancing current scientific knowledge on how leakage from GCS may impact the environment, improving predictions of CO(2)-induced geochemical changes in the subsurface, and facilitating science-based decision- and policy-making on risk associated with geologic carbon sequestration.

Reduction of Chromium(VI) mediated by zero-valent magnesium under neutral pH conditions.

In an effort to assess the potential use of ZVMg in contaminant treatments, we examined Cr(VI) reduction mediated by ZVMg particles under neutral pH conditions. The reduction of Cr(VI) was tested with batch experiments by varying [Cr(VI)](0) (4.9, 9.6, 49.9 or 96.9 µM) in the presence of 50 mg/L ZVMg particles ([Mg(0)](0) = 2.06 mM) at pH 7 buffered with 50 mM Na-MOPS. When [Cr(VI)](0) = 4.9 or 9.6 µM, Cr(VI) was completely reduced within 60 min. At higher [Cr(VI)](0) (49.9 or 96.9 µM), by contrast, the reduction became retarded at >120 min likely due to rapid ZVMg dissolution in water and surface precipitation of Cr(III) on ZVMg particles. Surface precipitation was observed only when [Cr(VI)](0) = 49.9 or 96.9 µM and increased with increasing [Cr(VI)](0). The effect of dissolved oxygen was negligible on the rate and extent of Cr(VI) reduction. Experimental results indicated that Cr(VI) was reduced not directly by ZVMg but by reactive intermediates produced from ZVMg-water reaction under the experimental conditions employed in this study. In addition, the observed rates of Cr(VI) reduction appeared to follow an order below unity (0.19) with respect to [Cr(VI)](0). These results imply that ZVMg-mediated Cr(VI) reduction likely occurred via an alternative mechanism to the direct surface-mediated reduction typically observed for other zero-valent metals. Rapid and complete Cr(VI) reduction was achieved when a mass ratio of [ZVMg](0):[Cr(VI)](0) ≥ 100 at neutral pH under both oxic and anoxic conditions. Our results highlights the potential for ZVMg to be used in Cr(VI) treatments especially under neutral pH conditions in the presence of dissolved oxygen.

Defluoridation from aqueous solutions by granular ferric hydroxide (GFH).

This research was undertaken to evaluate the feasibility of granular ferric hydroxide (GFH) for fluoride removal from aqueous solutions. Batch experiments were performed to study the influence of various experimental parameters such as contact time (1 min-24h), initial fluoride concentration (1-100 mgL(-1)), temperature (10 and 25 degrees C), pH (3-12) and the presence of competing anions on the adsorption of fluoride on GFH. Kinetic data revealed that the uptake rate of fluoride was rapid in the beginning and 95% adsorption was completed within 10 min and equilibrium was achieved within 60 min. The sorption process was well explained with pseudo-first-order and pore diffusion models. The maximum adsorption capacity of GFH for fluoride removal was 7.0 mgg(-1). The adsorption was found to be an endothermic process and data conform to Langmuir model. The optimum fluoride removal was observed between pH ranges of 4-8. The fluoride adsorption was decreased in the presence of phosphate followed by carbonate and sulphate. Results from this study demonstrated potential utility of GFH that could be developed into a viable technology for fluoride removal from drinking water.

Metal release from bottom sediments of Ocoee Lake No. 3, a primary catchment area for the Ducktown Mining District.

Ocoee Lake No. 3 is the first reservoir receiving suspended sediments contaminated with trace metals discharged by acid mine effluents from the Ducktown Mining District, Tennessee. Bottom sediments (0-5 cm) from the lake were sampled to assess the potential for future adverse environmental effects if no remediation controls or activities are implemented. The sediments were found to include a major component (173 +/- 19 g kg(-1)) that dissolved in 6 mol L(-1) HCl within 24 h. This acid-soluble and relatively labile fraction contained high concentrations of Fe (460 +/- 40 g kg(-1)), Al (99 +/- 11 g kg(-1)), Mn (10 +/- 8 g kg(-1)), Cu (2000 +/- 700 mg kg(-1)), Zn (1300 +/- 200 mg kg(-1)), and Pb (300 +/- 200 mg kg(-1)). When the pH of water in contact with the sediment was decreased experimentally from 6.4 to 2.6, the concentrations of dissolved trace metals increased by factors of 2200 for Pb, 160 for Cu, 21 for Zn, 9 for Cd, 8 for Ni, and 5 for Co. The order in which metals were released with decreasing pH was the reverse of that reported for pH-dependent sorption of these metals in upstream systems. Substantial release of trace metals from the sediment was observed even by a modest decrease of pH from 6.4 to 5.9. Therefore, the metal-rich sediment of the lake should be considered as potentially hazardous to bottom-dwelling aquatic species and other organisms in the local food chain. In addition, if the reservoir is dredged or if the dam is removed, the accumulated sediment may have to be treated for recovery of sorbed metals.

Oxidative dissolution of chromium(III) hydroxide at pH 9, 3, and 2 with product inhibition at pH 2.

Hexavalent chromium, Cr(VI), can be immobilized under neutral to alkaline conditions by reduction to Cr(III); similarly, the mobility of naturally occurring Cr in soils and sediments can be limited by its occurrence in the +III oxidation state. Conversely, the oxidation of Cr(IIi) to Cr(VI) increases both its toxicity and often its mobility. Dissolution of Cr-(OH)3(s) in 0.01 M NaNO3 suspensions was examined in batch experiments in the presence and absence of the strong oxidant sodium hypochlorite (NaOCI). Dissolution of Cr(OH)3(s) (1.0 g/L) was accelerated in the presence of excess strong oxidant (20 mM) at pH 9 by a factor of ca. 200 and to a lesser extent at pH 2 and 3. Linear kinetics of oxidative dissolution was observed at pH 9 and 3. In contrast, the rate of Cr release at pH 2 decreased rapidly with time, and within 2.5 h, the dissolution reaction was completely inhibited. Under oxidizing conditions, Cr released into solution is expected to be present as Cr(VI), which sorbs strongly to Cr(OH)3(s) at low pH. Cr(VI) sorption followed a Langmuir isotherm and reached maximum sorption densities of 308 +/- 8 and 271 +/- 10 micromol/g at pH 3 and 2, respectively. However, sorption of Cr(VI) (putatively formed during oxidative dissolution) cannot explain the observed inhibition of the reaction because (1) sorption occurs at both pH 2 and 3 but inhibition only at pH 2 and (2) preequilibration of Cr(OH)3(s) with Cr(VI) did not affectthe rate of dissolution observed upon the addition of the oxidant. Thus, we hypothesize that the inhibition of (net) oxidative dissolution at pH 2 may be the result of secondary precipitation of a chromic hydroxy chromate phase.