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.

A multi-scale assessment of the impact of salinity on the desorption of chromate from hematite: Sea level rise implications.

The solubility and transport of Cr(VI) is primarily controlled by adsorption-desorption reactions at the surfaces of soil minerals such as iron oxides. Environmental properties such as pH, ionic strength, and ion competition are expected to affect the mobility and fate of Cr(VI). Sea level rise (SLR), and consequent seawater intrusion, is creating a new biogeochemical soil environment at coastal margins, potentially impacting Cr(VI) retention at contaminated sites. We employed in-situ ATR-FTIR spectroscopy and DFT calculations to investigate at the molecular level the adsorption of Cr(VI) on the hematite surface and its desorption by sulfate, as a function of pH and ionic strength. We further used a batch experiment to assess Cr(VI) desorption at varying artificial seawater (ASW) concentrations. IR results demonstrate the complexity of Cr(VI) adsorption, showing a combination of monodentate inner-sphere complexation at high pH and dichromate outer-sphere (∼75%) at low pH. The Cr(VI)-complexes exhibited desorption induced by increasing pH values (58% of desorption) and sulfate competition (∼40% desorption). ASW desorbed ∼20% more Cr(VI), even at just 1% concentration. Our findings provide insight into Cr(VI)-adsorption complexation that controls the retention and remobilization of Cr(VI) on Fe-oxide minerals. The results point to an elevated risk of Cr(VI) mobilization in contaminated soils affected by SLR.

The adsorption of arsenate and p-arsanilic acid onto ferrihydrite and subsequent desorption by sulfate and artificial seawater: Future implications of sea level rise.

Sea level rise (SLR) is estimated to impact 25% of the world's population along coastal areas leading to an increase in saltwater intrusion. Consequently, changes in the soil biogeochemistry of currently non-saline and/or well-drained soils due to saltwater intrusion are of major concern. Saltwater intrusion is expected to affect farmland across large broiler producer regions, where large amounts of manure containing organic arsenicals were applied over the past decades. To determine how SLR may impact the speciation and mobility of adsorbed inorganic and organic As, we used in situ real-time attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to determine the adsorption and desorption mechanisms of As(V) and 4-aminophenylarsonic (p-ASA, a poultry feed additive) on ferrihydrite (Fh) in the presence of sulfate at varying pH. The adsorption of As(V) and p-ASA increased at lower pH, with As(V) showing IR features consistent with the formation of inner-sphere of As-Fh surface complexes, while p-ASA also formed others structures as H-bonded As-surface complexes, likely mediated by outer-sphere complexes, based on our FTIR and batch experiments data. No observable As(V) or p-ASA desorption from the Fh surface was promoted by sulfate, however sulfate adsorption on the Fh surface was remarkably larger for p-ASA than for As(V). Complimentary, we carried out batch studies of As(V) and p-ASA desorption by Fh, using artificial seawater (ASW) at varying concentrations. The 1% ASW desorbed ∼10% of initially sorbed p-ASA, while at 100% ASW desorbed ∼40%. However, <1% of As(V) was desorbed by 1% ASW solution and only ∼7.9% were desorbed at 100% ASW. The spectroscopic data support the more extensive desorption of p-ASA compared to As(V) observed in batch experiments, suggesting that organoarsenicals may be easily desorbed and, after conversion to inorganic forms, pose a risk to water supplies.

Immobilization of lead by amendments in a mine-waste impacted soil: Assessing Pb retention with desorption kinetic, sequential extraction and XANES spectroscopy.

Chemical stabilization is an in-situ remediation that uses amendments to reduce contaminant availability in polluted soils. Rates of phosphate, lime, biochar, and biosolids were evaluated as affecting Pb speciation and mobility in soil samples of a mining area located in Vazante, state of Minas Gerais, Brazil. Chemical and mineralogical characterization, desorption kinetics, sequential extraction, leaching evaluation in columns and speciation using X-ray absorption near edge structure were performed. Pb adsorbed on bentonite and on anglesite were the predominant species in the unamended soil. The treatments with phosphate and lime transformed part of the Pb species to pyromorphite. Conversely, part of Pb species was transformed to Pb adsorbed on citrate in the soil amended with biochar, while PbCl2 was formed in soil samples amended with biosolids. Phosphate and lime increased the Pb extracted in the residual fraction, thus showing that more recalcitrant species, such as pyromorphite, were formed. Biosolids and biochar treatments decreased the Pb in the residual fraction, and the fraction associated to organic matter increased after the addition of biosolids. Phosphate and lime were effective to immobilize Pb and to decrease Pb desorption kinetics, but the organic amendments increased the desorption kinetics of Pb in all rates applied. The soil amended with phosphate decreased the Pb leached in the experiment with leaching columns.

The molecular insights into protein adsorption on hematite surface disclosed by in-situ ATR-FTIR/2D-COS study.

Proteins are of ubiquitous interest in the Life Sciences but are of interest in the Geosciences as well because of the significant role these compounds play in the biogeochemical cycling of trace and nutrient elements. Structural changes resulting from the adsorption of proteins onto mineral surfaces may alter protein biological function and other environmental interactions. Iron oxides are major sinks of a range of environmental elements including organic compounds. In this study, the adsorption of the broadly studied model protein BSA onto the hematite mineral surface was characterized as a function of pH, ionic strength, and BSA concentration using in-situ Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy. BSA lost the α-helix and gain ß-sheets in the secondary structure during adsorption on hematite. BSA adsorption was maximum at pH 5, a value close to the BSA isoelectric point (~ pH 5), and lower at pH 4 and pH 7. Increasing ionic strength decreased to total BSA adsorption. Two-dimensional correlation spectroscopy analysis of the ATR-FTIR spectra revealed that higher initial BSA concentration and the consequent higher BSA surface loading enhanced BSA adsorption by protein-protein interaction, which less ordered structures changes into more compact forms decrease, hence compacting the structural arrangement and could promoting multilayers/aggregation formation on the mineral surface. The activity of enzymes following adsorption on mineral surfaces requires further study.

Hausmannite as potential As(V) filter. Macroscopic and spectroscopic study of As(V) adsorption and desorption by citric acid.

Arsenic (As) is a toxic element that leads the list of human health threats and is one of the priority contaminants in soil and water. In order to remove As(V) and/or reduce its mobility, filters and amendments with high affinity for As(V) adsorption are used in drinking water treatment or directly applied to the soil, thereby promoting its immobilization. Hausmannite and hematite were compared by in-situ Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) spectroscopy and batch experiments for evaluating As(V) adsorption and sequential desorption by citrate. The pH and contact time were used as variables. Hausmanite adsorbed more As(V) than hematite. As(V) was adsorbed on the mineral surface of simultaneously inner- and outer-sphere species. Inner-sphere bidentate complex form preferentially at high pH, early adsorption time and low surface loading, while the monodentate species should be responsible to increase total As(V) adsorption at low pH, later adsorption kinetics and higher As(V) surface loading. Citrate was effective in causing As(V) desorption at higher citric acid concentrations and higher pH values. After a long time of incubation, the neogenesis of a manganite by hausmnannite oxidation was observed. Concomitantly, less As(V) was desorbed by citrate desorption, even in the presence of high citric acid concentrations. Hausmannite was an efficient mineral for As(V) removal and immobilization.