Coupling Molecular-Scale Spectroscopy with Stable Isotope Analyses to Investigate the Effect of Si on the Mechanisms of Zn-Al LDH Formation on Al Oxide.

While silicate has been known to affect metal sorption on mineral surfaces, the mechanisms remain poorly understood. We investigated the effects of silicate on Zn sorption onto Al oxide at pH 7.5 and elucidated the mechanisms using a combination of X-ray absorption fine structure (XAFS) spectroscopy, Zn stable isotope analysis, and scanning transmission electron microscopy (STEM). XAFS analysis revealed that Zn-Al layered double hydroxide (LDH) precipitates were formed in the absence of silicate or at low Si concentrations (≤0.4 mM), whereas the formation of Zn-Al LDH was inhibited at high silicate concentrations (≥0.64 mM) due to surface-induced Si oligomerization. Significant Zn isotope fractionation (Δ66Znsorbed-aqueous = 0.63 ± 0.03‰) was determined at silicate concentrations ≥0.64 mM, larger than that induced by sorption of Zn on Al oxide (0.47 ± 0.03‰) but closer to that caused by Zn bonding to the surface of Si oxides (0.60-0.94‰), suggesting a presence of Zn-Si bonding environment. STEM showed that the sorbed silicates had a close spatial coupling with γ-Al2O3, indicating that >Si-Zn inner-sphere complexes (">" denotes surface) likely bond to the γ-Al2O3 surface to form >Al-Si-Zn ternary inner-sphere complexes. This study not only demonstrates that dissolved silicate in the natural environment plays an important role in the fate and bioavailability of Zn but also highlights the potential of coupled spectroscopic and isotopic methods in probing complex environmental processes.

Iron Speciation in Organic Matter Fractions Isolated from Soils Amended with Biochar and Organic Fertilizers.

The role and distribution of iron (Fe) species in physical soil fractions have received remarkably little attention in field-scale systems. Here, we identify and quantify the Fe phases into two fractions (fine sand, FSa, and fine silt and clay, FSi + Cl), isolated from an agricultural soil unamended and amended with different organic materials, by Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The linear combination fitting and wavelet transform of EXAFS data revealed noticeable differences between unamended FSa and FSi + Cl fractions. Specifically, the FSi + Cl fraction was mainly characterized by ferrihydrite (48%) and Fe(III)-soil organic matter (SOM) complexes (37%), whereas in the FSa fraction, ferrihydrite still represented a major phase (44%), with a lower contribution from Fe(III)-SOM (18%). In the FSa fraction, the addition of the organic amendments resulted in an increase of Fe-SOM complexes (31-35%) and a decrease of ferrihydrite (28-29%). By contrast, in the amended FSi + Cl fractions, the added organic matter led to negligible changes in percent ferrihydrite. Therefore, regardless of the amendment type, the addition of organic matter to soil increased the capability of the coarse fraction (FSa) to stabilize organic carbon, thus pointing out that the role of FSa in carbon sequestration in agricultural soils at a global scale may be overlooked.

Natural speciation of nickel at the micrometer scale in serpentine (ultramafic) topsoils using microfocused X-ray fluorescence, diffraction, and absorption.

Serpentine soils and ultramafic laterites develop over ultramafic bedrock and are important geological materials from environmental, geochemical, and industrial standpoints. They have naturally elevated concentrations of trace metals, such as Ni, Cr, and Co, and also high levels of Fe and Mg. Minerals host these trace metals and influence metal mobility. Ni in particular is an important trace metal in these soils, and the objective of this research was to use microscale (µ) techniques to identify naturally occurring minerals that contain Ni and Ni correlations with other trace metals, such as Fe, Mn, and Cr. Synchrotron based µ-XRF, µ-XRD, and µ-XAS were used. Ni was often located in the octahedral layer of serpentine minerals, such as lizardite, and in other layered phyllosilicate minerals with similar octahedral structure, such as chlorite group minerals including clinochlore and chamosite. Ni was also present in goethite, hematite, magnetite, and ferrihydrite. Goethite was present with lizardite and antigorite on the micrometer scale. Lizardite integrated both Ni and Mn simultaneously in its octahedral layer. Enstatite, pargasite, chamosite, phlogopite, and forsterite incorporated various amounts of Ni and Fe over the micrometer spatial scale. Ni content increased six to seven times within the same 500 µm µ-XRD transect on chamosite and phlogopite. Data are shown down to an 8 µm spatial scale. Ni was not associated with chromite or zincochromite particles. Ni often correlated with Fe and Mn, and generally did not correlate with Cr, Zn, Ca, or K in µ-XRF maps. A split shoulder feature in the µ-XAS data at 8400 eV (3.7 Å-1 in k-space) is highly correlated (94% of averaged LCF results) to Ni located in the octahedral sheet of layered phyllosilicate minerals, such as serpentine and chlorite-group minerals. A comparison of bulk-XAS LCF to averaged µ-XAS LCF results showed good representation of the bulk soil via the µ-XAS technique for two of the three soils. In the locations analyzed by µ-XAS, average Ni speciation was dominated by layered phyllosilicate and serpentine minerals (76%), iron oxides (18%), and manganese oxides (9%). In the locations analyzed by µ-XRD, average Ni speciation was dominated by layered phyllosilicate, serpentine, and ultramafic-related minerals (71%) and iron oxides (17%), illustrating the complementary nature of these two methods.

Competitive sorption of Ni and Zn at the aluminum oxide/water interface: an XAFS study.

Trace metals (e.g. Ni, Zn) leached from industrial and agricultural processes are often simultaneously present in contaminated soils and sediments. Their mobility, bioavailability, and ecotoxicity are affected by sorption and cosorption at mineral/solution interfaces. Cosorption of trace metals has been investigated at the macroscopic level, but there is not a clear understanding of the molecular-scale cosorption processes due to lack of spectroscopic information. In this study, Ni and Zn cosorption to aluminum oxides (γ-Al2O3) in binary-sorbate systems were compared to their sorption in single-sorbate systems as a function of pH using both macroscopic batch experiments and synchrotron-based X-ray absorption fine structure spectroscopy. At pH 6.0, Ni and Zn were sorbed as inner-sphere surface complexes and competed for the limited number of reactive sites on γ-Al2O3. In binary-sorbate systems, Ni had no effect on Zn sorption, owning to its lower affinity for the metal oxide surface. In contrast, Zn had a higher affinity for the metal oxide surface and reduced Ni sorption. At pH 7.5, Ni and Zn were sorbed as mixed-metal surface precipitates, including Ni-Al layered double hydroxides (LDHs), Zn-Al LDHs, and likely Ni-Zn-Al layered triple/ternary hydroxides. Additionally, at pH 7.5, Ni and Zn do not exhibit competitive sorption effects in the binary system. Taken together, these results indicated that pH critically influenced the reaction products, and provides a crucial scientific basis to understand the potential mobility, bioavailability, and ecotoxicity of Ni and Zn in natural and contaminated geochemical environments.

Structural Differentiation between Layered Single (Ni) and Double Metal Hydroxides (Ni-Al LDHs) Using Wavelet Transformation.

Layered double hydroxides (LDHs) are anionic clays important in disciplines such as environmental chemistry, geochemistry, and materials science. Developments in signal processing of extended X-ray absorption fine structure (EXAFS) data, such as wavelet transformation (WT), have been used to identify transition metals and Al present in the hydroxide sheets of LDHs. The WT plots of LDHs should be distinct from those of isostructural single metal hydroxides. However, no direct comparison of these minerals appears in the literature using WT. This work systematically analyzes a suite of Ni-rich mineral standards, including Ni-Al LDHs, single metal Ni hydroxides, and Ni-rich silicates using WT. The results illustrate that the WT plots for α-Ni(OH)2 and Ni-Al LDHs are often indistinguishable from each other, with similar two-component plots for the different mineral types. This demonstrates that the WT of the first metal shell often cannot be used to differentiate an LDH from a single metal hydroxide. Interlayer anions adsorbed to the hydroxide sheet of α-Ni(OH)2 affect the EXAFS spectra and are not visible in the FT but are clearly resolved and discrete in the WT.

Sea-level rise and arsenic-rich soils: A toxic relationship.

In the United States, dangerously high arsenic (As) levels have been found in drinking water wells in more than 25 states, potentially exposing 2.1 million people to drinking water high in As; a known carcinogen. The anticipated sea-level rise (SLR) is expected to alter soil biogeochemical and hydrological conditions, potentially impacting their ability to sequester As. In our study of coastal Wilmington, DE, an area projected to experience a 1 -meter SLR by 2100, we examined the spatial distribution, speciation, and release possibilities of As due to SLR. To understand the complex dynamics at play, we employed a comprehensive approach, including bulk and micro X-ray absorption spectroscopy measurements, hydrological pattern evaluation, and macroscopic stirred-flow experiments. Our results suggest that introducing reducing and saline conditions can increase As release in both river water and seawater inundation scenarios, most likely due to ionic competition and the dissolution of As-bearing Fe/Mn oxides. Regardless of the salinity source, the released As concentrations consistently exceeded the EPA threshold for drinking water. Our results provide valuable insights for developing appropriate remedial and management strategies for this site and numerous others facing similar environmental challenges. ENVIRONMENTAL IMPLICATION: With nearly two hundred million individuals living within coastal flood plains and with two million square kilometers of land and one trillion dollars' worth of assets lying less than 1 m above current sea level, sea-level rise (SLR) is one of the significant socio-economic threats associated with global warming. Arsenic is a prevalent contaminant in coastal areas impacted by industrial activities, many of which are susceptible to being impacted by SLR. This study examines SLR's impact on arsenic fate and speciation in a densely populated coastline in Wilmington, DE, expecting 1 meter of SLR by 2100.

Zinc speciation in highly weathered tropical soils affected by large scale vegetable production.

Agriculture in highly weathered tropical soils often requires considerable application of lime and fertilizers to ensure satisfactory plant nutrient levels. The consequences of these continue long-term applications is not well understood may induce changes in soil chemical properties, the abundance, and speciation of potentially toxic trace element and as well as of micronutrients in agriculture soils. In this study, we evaluated the adsorption (at pH 5) and speciation of Zn in tropical soils (both agricultural and native vegetation) as a function of fertilization and contact time using chemical fractionation analyses and X-ray absorption spectroscopy. The soils overall had high Zn adsorption capacities (∼ 700 mg kg-1), but the agricultural soil was approximately 30 % higher than of the soil under native vegetation, and the proportion of Zn in the mobile fraction was 35 % in native vegetation and 21 % in agricultural soils. Zn speciation via linear combination analysis showed a strong relationship with soil mineralogical composition and reveled that Zn associated with organic matter decreased while Zn associated with P increased after the conversion of soils from native vegetation to highly fertilized soil. Aluminosilicate soil minerals were identified as major sinks of soil Zn, accounting for 34 % of total Zn retention regardless of soil origin and land use. Association of Zn with phosphate (i.e., hopeite) was observed in the agricultural soil samples, which might be an unexpected Zn-bearing mineral in highly weathered tropical soils and could have impacts on Zn plant nutrition.

Influence of clay mineral weathering on green rust formation at iron-reducing conditions.

Green rusts (GR) are important drivers for trace metal and nutrient cycling in suboxic environments. We investigated whether green rusts would incorporate aluminum (Al) or other elements from naturally-formed clay minerals containing easily-weatherable clay minerals (e.g. mica, interlayered clays). We isolated the clay minerals from a Matapeake silt loam soil by removal of silt and sand, organic matter, and reducible oxides to study mechanisms of interaction between Fe(II) and soil-sourced clay minerals. We conducted batch Fe(II) sorption experiments at multiple near-neutral pHs (6.5-7.5) and reaction times (2 h-365 days). Mineral transformations were characterized by selective extractions, X-ray diffraction (XRD), and Fe X-ray absorption spectroscopy (XAS) analyzed by shell-fitting and linear combination fitting (LCF) with natural and synthetic standards. Clay mineral fraction contained a mixture of quartz, kaolinite, interlayered vermiculite, mica, and chlorite with significant structural Fe (2.6% wt). Uptake of Fe(II) increased with pH and kinetics were rapid until 5 days, followed by slow continuous Fe(II) uptake. Citrate-bicarbonate desorption kinetics from Fe(II) sorbed clay released more Al and silicon (Si) compared with unreacted soil clay fraction whereas magnesium (Mg) and potassium (K) were unaffected. Citrate-bicarbonate extracted Fe contained more Fe(II) than an ideal GR with an Fe(II)/Fe(III) molar ratio of 5.50. Analysis of the Fe EXAFS by both LCF and shell fitting was best modeled as a combination of Fe(III)-clay reduction to Fe(II) and precipitation of GR and Fe(II)-Al LDH. After 7 days of Fe(II) sorption, LCF identified 55.2% total Fe in clay, 33.4% GR(Cl) and 11.4% Fe(II)-Al LDH. These results provide novel evidence of Fe(II)-Al LDHs precipitating on naturally-formed soil clay minerals as a minor phase to GR. The geochemical implications are that GRs formed in soils and sediments should be considered to have Al and Si as well as Mg substitutions affecting their structure and reactivity.

Mobility and bioaccessibility of arsenic (As) bound to titanium dioxide (TiO2) water treatment residuals (WTRs).

This work systematically describes arsenic mobility and potential bioaccessibility of arsenic-enriched titanium dioxide water treatment residuals (TiO2 WTRs) by employing a suite of wet chemical experiments and spectroscopic measurements. Specifically, Environmental Protection Agency (EPA) digestion method 3051a indicated <3% of total arsenic in the solid phase was released, and arsenic assessed by EPA method 1340 for bioaccessibility was below detection limits. A novel finding is while the arsenic appeared to be stable under highly acidic digestion conditions, it is in fact highly mobile when exposed to simple phosphate solutions. On average, 55% of arsenic was extracted from all samples during a 50-day replenishment study. This was equivalent to 169 mg kg-1 arsenic released from the solid phase. Macroscopic desorption experiments indicated arsenic likely formed inner-sphere bonds with the TiO2 particles present in the samples. This was confirmed with X-ray absorption spectroscopy (XAS), where an interatomic distance of 3.32 Å and a coordination number (CN) of 1.79 titanium atoms were determined. This translates to a configuration of arsenic on TiO2 surfaces as a bidentate binuclear inner-sphere complex. Thus, both macroscopic and spectroscopic data are in agreement. During incubation experiments, arsenic(V) was actively reduced to arsenic(III); the amount of arsenic(III) in solution varied from 8 to 38% of total dissolved arsenic. Lastly, elevated concentrations and mobility of vanadium in these systems merit further investigation. The high mobility of arsenic and its potential for reduction when reintroduced into the environment, particularly in agriculturally important areas, presents an important risk when waste products are not properly managed.

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Sea-level-rise-induced flooding drives arsenic release from coastal sediments.

Sea-level rise (SLR) has a vital influence on coastal hydrogeological systems, biogeochemical processes, and the fate of coastal contaminants. However, the effects of SLR-induced perturbations on the mobilization of coastal pollutants are not fully understood. In this study, the impact of SLR-induced flooding on the concentration and speciation of arsenic and selected hazardous chemicals is investigated using exceedingly contaminated sediments (5-6% As) collected from an urban coastal site in Wilmington, DE, USA. The release of contaminants from sediments was monitored before, during, and after flooding with different intensities (bottom shear stresses) through laboratory-based erosion chamber experiments. Significantly increased release of As (up to 150%) and NO3 (up to 50%) from sediments at shear stress levels typically measured in estuaries were found. The release of toxic chemicals from contaminated coastal sediments is thus not restricted to extreme flooding events but can occur throughout the year. The results also suggest that the dissolved concentrations of pollutants continue to be considerably high even after the flooding. SLR-induced flooding can hence increase the release of contaminants not only during erosion events but over longer timescales. The release mechanism proposed here contributes to improving the risk assessment of coastal water pollution as climate change and SLR continue to occur.

Metal (hydr)oxide surface precipitates and their effects on potassium sorption.

Surface precipitation has been shown to occur on rapid time scales in clay and metal oxide mineral systems. The formation of surface precipitates is hypothesized to present new potential sorption sites for potassium (K), where K can become incorporated into newly formed interlayer spaces (e.g., between tetrahedral-octahedral-tetrahedral stacked sheets). The objective of this study is to determine the effects of newly formed mineral surface precipitates on K sorption. Potassium adsorption experiments were conducted by utilizing Al2O3 and SiO2 sorbents in the presence of various cations (magnesium, zinc, and nickel) that helped to catalyze the formation of surface precipitates. Dissolved concentrations of elements were monitored via inductively coupled plasma optical emission spectrometry (ICP-OES). Solids were characterized via X-ray diffraction (XRD), and K surface complexation was analyzed via X-ray absorption near edge structure (XANES) spectroscopy. X-ray diffraction analysis indicated bayerite, layered double hydroxides (LDH), and silicated LDH were formed as reaction products, thus creating new surface sites for potential K adsorption. The presence of Si increased K adsorption perhaps due to its role in the formation of LDH surface precipitates. When the differences between observed and theoretical surface area normalized K sorption densities were averaged, a 31% increase in K adsorption was observed in the presence of Si. XANES analysis indicated that the binding mechanism of K to Si is different than that of K to Al, perhaps due to the presence of inner-sphere complexation of K to Al-oxide. Samples reacted for one month versus one week yielded more intense XANES post-edge peaks which indicated that the K sorption complex changes over time. Overall, our findings provide novel insights into the mechanisms of K fixation in soil and has high implication in providing improved K fertilizer recommendation to growers.

A porous ceramic particle with or without a preservative blend did not impair apparent digestibility of macro- and micro-nutrients of postweaned pigs.

The objective of this study was to determine the effects of supplementing a commercial porous ceramic clay particle, with or without a blend of preservatives, on the performance and nutrient digestibility of weanling pigs. Fifteen weanling pigs of the Yorkshire, Landrace, and Duroc breeds were blocked by breed and randomly assigned to one of three treatments (n = 5): (1) Control, non-medicated diet with no additional feed additives (CON); (2) PowerGuard, basal diet with 0.25% of the DM consisting of a ceramic particle mixed into the pelleted feed (PG; MB Nutritional Sciences, Lubbock, TX, 79403); or (3) Power Guard + a blend of preservatives, basal diet with 0.3% of the DM consisting of the ceramic clay and preservatives mixed into the pelleted feed (PG-D). The facility was temperature controlled with an average temperature of 28.5 °C. Pigs were offered ad libitum access to feed and water and were housed individually in elevated crates. Body weights were collected upon enrollment on day 0 and at the end of the observation period on day 18. On day 15 , a 72-h total feed and fecal collection period began. Feed and fecal samples were analyzed for DM, CP, Ash, OM, ADF, NDF, zinc, copper, thiamin (vitamin B1), and retinol (vitamin A). Liver samples were collected immediately after harvest and frozen for later mineral analysis. Data were analyzed using Proc Mixed in SAS with dietary group as the main effect and block as the random effect (SAS 9.4, Cary, NC). There were no treatment differences in performance measures including final BW, ADG, or G:F (P ≥ 0.701). There were no treatment differences in diet nutrient digestibility for DM, CP, Ash, OM, ADF, or NDF (P ≥ 0.312). Additionally, there were no treatment effects on zinc, copper, or retinol digestibility (P ≥ .298); however, thiamin inclusion rate was increased for the PG-D treatment, thus leading to an increased digestibility for thiamin (P = 0.018) in the PG-D treatment. There were no treatment differences in hepatic mineral concentrations (P ≥ 0.532); however, there was a tendency for pigs fed PG-D to have increased hepatic concentrations of lead and mercury when compared with both PG and CON pigs (P ≤ 0.066). In summary, supplementation of a commercial ceramic particle with or without a blend of preservatives to weaned pigs did not affect performance or apparent nutrient digestibility.

Combining zinc desorption with EXAFS speciation analysis to understand Zn mobility in mining and smelting affected soils in Minas Gerais, Brazil.

Zinc contents exceeding regulatory levels have been documented in several areas in Brazil and elsewhere, especially in sites surrounding mining and smelting sites. Studies involving Zn release and speciation are keys to assess the mobility and bioavailability and thus the potential ecological risk of this element. This study evaluated Zn desorption and speciation from soils affected by mining (soils from a mine area, classified as Technosols) and smelting (mine tailing) activities in Brazil with high total Zn contents, ranging from 1.8 to 8.2%, using a stirred-flow approach and synchrotron-based X-ray absorption spectroscopy (XAS), in order to better assess Zn availability and mobility in these environments. The exchangeable fraction, extracted by 0.1 M CaCl2 solution, represented only a small (<0.5%) portion of the total Zn from soils of the mining site, while accounting for ~80% from tailings of the smelting site. In the mine area, X-ray absorption fine structure (XAFS) showed that Zn was associated with hemimorphite, Zn-ferrihydrite, Zn-phyllosilicates (Zn-kerolite), and Zn-layered double hydroxides (Zn-LDH); this is the first time these Zn precipitate/sorbed forms have been detected in Brazilian mining soils, which have been exposed to tropical conditions. The formation of these insoluble phases of Zn could explain the low Zn desorption from these soils, taking into consideration that Zn-ferrihydrite, Zn-kerolite, and Zn-LDH can lead to a significant decrease of the exchangeable/mobile fraction of Zn in soils. The higher amount of Zn desorbed (⁓80%) from the tailing material located in the smelting site could be attributed to the predominance of weakly bound forms of Zn (~70%). These findings were also seen by analyzing the Fourier Transform (FT) and Wavelet Transform (WT). This study has shown that combining EXAFS analyses with desorption extraction is relevant to better understand Zn mobility and how it is related to Zn speciation.

Cadmium speciation and release kinetics in a paddy soil as affected by soil amendments and flooding-draining cycle.

Cadmium bioavailability in paddy soils is strongly affected by flooding-draining cycle. In this study, we used synchrotron-based X-ray absorption spectroscopy and a stirred-flow method to investigate the effects of flooding-draining and amendments of CaCO3 and CaSO4 on Cd speciation and release kinetics from a Cd-spiked paddy soil (total Cd concentration of 165 mg kg-1). Extended X-ray absorption fine structure analysis showed that Cd was predominantly bound to non-iron-clay minerals (e.g. Cd-kaolinite, Cd-illite, and Cd-montmorillonite, accounting for 60-100%) in the air-dried soil and 1- or 7-day flooded samples. After prolonged flooding (30 and 120 days), Cd-iron mineral complexes (e.g. Cd bound to ferrihydrite and goethite) became the predominant species (accounting for 52-100%). Stirred-flow kinetic analysis showed that both prolonged flooding and the amendments with CaCO3 and CaSO4 decreased the maximum amount and the rate coefficient of Cd release. However, the effect of prolonged flooding was reversed after a short period of draining, indicating that although Cd was immobilized during flooding, it became mobile rapidly after the soil was drained, possibly due to pH decrease and rapid oxidation of CdS. The effects of the amendments on Cd uptake in rice plants were tested in a pot experiment using the same paddy soil without Cd spiking (total Cd 2.1 mg kg-1). Amendment with CaCO3 and, to a lesser extent, CaSO4, decreased the Cd accumulation in two cultivars of rice. The combination of CaCO3 amendment and a low Cd accumulating cultivar was effective at limiting grain Cd concentration to below the 0.2 mg kg-1 limit.

Mechanistic insights into iodine enrichment in groundwater during the transformation of iron minerals in aquifer sediments.

Long-term intake of groundwater with elevated iodine concentration can cause thyroid dysfunction in humans; however, little is known on the mechanisms controlling the fate of iodine in groundwater systems. In this study, the groundwater and aquifer sediment samples from the Datong basin, a geologic iodine-affected area, were collected to perform the batch incubation experiments to understand the release and enrichment of iodine in groundwater systems. The results showed that the groundwater from the deep confined aquifer had a total iodine concentration of 473 µg/L, higher than that of shallow groundwater, and iodide is the dominant species of iodine. The deep confined aquifer was characterized by the reducing conditions. Meanwhile, a higher ratio of Fe(II) to total Fe was observed in bulk deep aquifer sediments (59%) in comparison with that of shallow sediments (33%). The results of batch incubation experiments showed that during the reductive transformation of Fe minerals in shallow aquifer sediments, iodide concentration in solution was gradually increasing from 24.7 to 101.5 µg/L after 10 days. It suggests that the transformation of Fe minerals in aquifer sediments acts as a diver causing the release of iodine from sediment into groundwater, which was further supported by the features Fe K-edge EXAFS before and after the batch experiments. Moreover, the changes in iodine species from iodate or organic iodine into iodide during the release further promotes the release of sediment iodine, which was supported by the developed geochemical models. The prevalence of reducing condition in deep aquifer favors the enrichment of released iodide. This study provides new insights into the mechanisms of iodide enrichment observed in deep confined aquifer.

The role of Fe(III) in soil organic matter stabilization in two size fractions having opposite features.

Soil organic matter (SOM) protection, stability and long-term accumulation are controlled by several factors, including sorption onto mineral surfaces. Iron (Fe) has been suggested as a key regulator of SOM stability, both in acidic conditions, where Fe(III) is soluble, and in near-neutral pH environments, where it precipitates as Fe(III) (hydr)oxides. The present study aimed to probe, by sorption/desorption experiments in which Fe was added to the system, the mechanisms controlling Fe(III)-mediated organic carbon (C) stabilization; fine silt and clay (FSi + Cl) and fine sand (FSa) SOM fractions of three soils under different land uses were tested. Fe(III) addition caused a decrease in the organic C remaining in solution after reaction, indicating an Fe-mediated organic C stabilization effect. This effect was two times larger for FSa than for FSi + Cl, the former fraction being characterized by both low specific surface area and high organic C content. The organic C retained in the solid phase after Fe-mediated stabilization has relatively low sensitivity to desorption. Moreover, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy indicated that Fe-mediated organic C stabilization can be mainly ascribed to the formation of complexes between carbohydrate OH functional groups and Fe oxides. These results demonstrate that the binding of labile SOM compounds to Fe(III) contributes to its preservation, and that the mechanisms involved (flocculation vs. coating) depend on the size fractions.

Formation of Cd precipitates on γ-Al2O3: Implications for Cd sequestration in the environment.

Apart from surface complexation, precipitation of minerals also plays an important role in reducing the mobility and transport of heavy metals in the environment. In this study, Cd(II) sorption species on surfaces of γ-Al2O3 at pH 7.5 were characterized using multiple techniques. Results show that in addition to adsorption complexes, Cd hydroxide phases (Cd(OH)2 precipitates and Cdx(OH)y polynuclear complexes) were formed at the initial stages of Cd(II) sorption and gradually transformed to CdCO3 with time. In addition, Cd(II) formed CdAl layered double hydroxide (LDH) on γ-Al2O3 under various conditions, independent of temperature and Cd loadings. The formation of Cd hydroxide phases and CdAl LDH could be ascribed to surface-induced precipitation because the bulk solution was undersaturated with respect to hydroxides. CdAl LDH formation on the Al-bearing mineral here is rather surprising because typically this occurs with elements of ionic radii similar to that of Al3+; this formation is unknown for metals such as Cd(II) with a much larger ionic radius. The thermodynamic feasibility of CdAl LDH formation was further confirmed by laboratory synthesis of CdAl LDH and density function theory (DFT) calculations. These results suggest that Cd precipitation on Al-bearing minerals can be an important mechanism for Cd immobilization in the natural environment. Additionally, the finding of CdAl LDH formation on Al-bearing minerals and the thermodynamic stability of CdAl LDH provides new insights into the remediation of Cd-polluted soils and aquatic systems.