Rodrigo C. Pereira, Pedro R. Anizelli, Eduardo Di Mauro, Daniel F. Valezi, Antonio Carlos S. da Costa, Cássia Thaïs B. V. Zaia, Dimas A. M. Zaia
{"title":"The effect of pH and ionic strength on the adsorption of glyphosate onto ferrihydrite","authors":"Rodrigo C. Pereira, Pedro R. Anizelli, Eduardo Di Mauro, Daniel F. Valezi, Antonio Carlos S. da Costa, Cássia Thaïs B. V. Zaia, Dimas A. M. Zaia","doi":"10.1186/s12932-019-0063-1","DOIUrl":"https://doi.org/10.1186/s12932-019-0063-1","url":null,"abstract":"<p>Although, glyphosate (<i>N</i>-(phosphonomethyl) glycine) is one of the most widely used herbicides in the world, its interaction with poorly crystalline iron oxides, such as ferrihydrite, is not well studied. In this research, we examined the adsorption of glyphosate onto ferrihydrite using infrared spectroscopy (FT-IR), electron paramagnetic resonance spectroscopy (EPR), adsorption kinetic models and adsorption isotherm models. The effect of pH and sodium chloride concentration on the adsorption of glyphosate onto ferrihydrite as well as the effect of extractors (CaCl<sub>2</sub> 0.010?mol?L<sup>?1</sup> and Mehlich) on the desorption of glyphosate were also evaluated. There are two important findings described in this work. First, 84% of adsorbed glyphosate strongly interacted to ferrihydrite as an inner-sphere complex and phosphate and amine groups are involved in this interaction. Second, an increase of sodium chloride salt concentration increased the adsorption of glyphosate onto ferrihydrite. The non-linear Langmuir model and pseudo second order model showed a good agreement of theoretical limit of glyphosate adsorbed onto ferrihydrite, 54.88?μg?mg<sup>?1</sup> and 48.8?μg?mg<sup>?1</sup>, respectively. The adsorption of glyphosate onto ferrihydrite decreased when the pH increased. Under the conditions used in this work, EPR spectra did not show dissolution of ferrihydrite. Surface area, pore volume and pH<sub>pzc</sub> of ferrihydrite decreased after adsorption of glyphosate.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"20 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2019-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-019-0063-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4948912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andreas Voegelin, Anna-Caterina Senn, Ralf Kaegi, Stephan J. Hug
{"title":"Reductive dissolution of As(V)-bearing Fe(III)-precipitates formed by Fe(II) oxidation in aqueous solutions","authors":"Andreas Voegelin, Anna-Caterina Senn, Ralf Kaegi, Stephan J. Hug","doi":"10.1186/s12932-019-0062-2","DOIUrl":"https://doi.org/10.1186/s12932-019-0062-2","url":null,"abstract":"<p>Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5?mM precipitate-Fe(III) using 10?mM Na-ascorbate as reductant, 5?mM bipyridine as Fe(II)-complexing ligand, and 10?mM MOPS/5?mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t<sub>50%</sub>) ranged from 1.5 to 39?h; spanning a factor 25 range. At loadings up to ~?0.2 P/Fe (molar ratio), phosphate decreased the t<sub>50%</sub> of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~?0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"20 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2019-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-019-0062-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4867141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Michael Schindler, Haley Mantha, Michael F. Hochella Jr.
{"title":"The formation of spinel-group minerals in contaminated soils: the sequestration of metal(loid)s by unexpected incidental nanoparticles","authors":"Michael Schindler, Haley Mantha, Michael F. Hochella Jr.","doi":"10.1186/s12932-019-0061-3","DOIUrl":"https://doi.org/10.1186/s12932-019-0061-3","url":null,"abstract":"<p>Mineralogical studies of contaminated soils affected by smelter emission and dust from mining activities indicate that minerals of the spinel group are one of the common hosts of metal-bearing contaminants. Spinel group minerals typically originate from high temperature processes, but an increasing number of studies indicate that metal-bearing spinel group minerals can also form under ambient Earth surface conditions in surficial soils. In this contribution to honor Donald Sparks, we show that the spinels Zn-bearing magnetite (Zn<sub>0.5</sub>Fe<sub>2.5</sub>O<sub>4</sub>) and minium (Pb<sub>3</sub>O<sub>4</sub>) form during low temperature alteration of Pb-bearing silica glass in surficial organic rich soils in proximity to a former Cu-smelter in Timmins, Ontario, Canada. The glass most likely formed during high-temperature processes and has been either emitted by the smelter or wind-blown from waste rock piles to near-by soils. The alteration of the glass by percolating pore solutions has resulted in the formation of large micrometer-size dendritic etch features and in nanometer-size dendritic alteration halos composed of nano-size prismatic crystals of Zn-rich magnetite and spherical nanoparticles of minium. Both spinel-type phases are embedded in an amorphous silica matrix which formed during the alteration of the glass at low temperature. A review on the occurrence of spinel-group minerals in smelter-affected soils or mine tailings indicates that the formation of these minerals under ambient Earth surface conditions is quite common and often results in the sequestration of contaminants such as Cu, Ni, Zn and Sb. The pedogenic spinels often occur as euhedral crystals in nano-size mineral assemblages within alteration features such as dendritic etch patterns, mineral surface coatings and mineralized organic matter. Their well-developed crystal forms indicate that (a) they have not formed during a rapid cooling process in a smelter or refinery which typically creates spherical particulate matter, and (b) they have not been part of particulate matter added via fluvial or Aeolian processes which most commonly yield anhedral morphologies. The formation of nano-size spinel-group minerals in low temperature environmental settings may lead to the long-term storage of metal(loid)s in mineral phases and their transport over vast distances via fluvial, alluvial and Aeolian processes.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"20 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2019-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-019-0061-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4544057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Onboard experiment investigating metal leaching of fresh hydrothermal sulfide cores into seawater","authors":"Shigeshi Fuchida, Jun-ichiro Ishibashi, Kazuhiko Shimada, Tatsuo Nozaki, Hidenori Kumagai, Masanobu Kawachi, Yoshitaka Matsushita, Hiroshi Koshikawa","doi":"10.1186/s12932-018-0060-9","DOIUrl":"https://doi.org/10.1186/s12932-018-0060-9","url":null,"abstract":"<p>We observed the initial release rate of metals from four fresh (i.e., without long time exposure to the atmosphere) hydrothermal sulfide cores into artificial seawater. The sulfide samples were collected by seafloor drilling from the Okinawa Trough by <i>D/V Chikyu</i>, powdered under inert gas, and immediately subjected to onboard metal-leaching experiments at different temperatures (5?°C and 20?°C), and under different redox conditions (oxic and anoxic), for 1–30?h. Zinc and Pb were preferentially released from sulfide samples containing various metals (i.e., Mn, Fe, Cu, Zn, Cd, and Pb) into seawater. Under oxic experimental conditions, Zn and Pb dissolution rates from two sulfide samples composed mainly of iron disulfide minerals (pyrite and marcasite) were higher than those from two other sulfide samples with abundant sphalerite, galena, and/or silicate minerals. Scanning electron microscopy confirmed that the high metal-releasing sample contained several galvanic couples of iron disulfide with other sulfide minerals, whereas the low metal-releasing sample contained fewer galvanic couples or were coated by a silicate mineral. The experiments overall confirmed that the galvanic effects with iron disulfide minerals greatly induce the initial release of Zn and Pb from hydrothermal sulfides into seawater, especially under warm oxic conditions.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0060-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4244700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Matthew G. Siebecker, Rufus L. Chaney, Donald L. Sparks
{"title":"Natural speciation of nickel at the micrometer scale in serpentine (ultramafic) topsoils using microfocused X-ray fluorescence, diffraction, and absorption","authors":"Matthew G. Siebecker, Rufus L. Chaney, Donald L. Sparks","doi":"10.1186/s12932-018-0059-2","DOIUrl":"https://doi.org/10.1186/s12932-018-0059-2","url":null,"abstract":"<p>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??<sup>?1</sup> 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.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0059-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4562593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrew W. Knight, Austen B. Tigges, Anastasia G. Ilgen
{"title":"Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement","authors":"Andrew W. Knight, Austen B. Tigges, Anastasia G. Ilgen","doi":"10.1186/s12932-018-0057-4","DOIUrl":"https://doi.org/10.1186/s12932-018-0057-4","url":null,"abstract":"<p>Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100?nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu<sup>2+</sup>), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4?nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu<sup>2+</sup> increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4?nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0057-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5009191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalytic oxidation of arsenite and reaction pathways on the surface of CuO nanoparticles at a wide range of pHs","authors":"Lingqun Zeng, Biao Wan, Rixiang Huang, Yupeng Yan, Xiaoming Wang, Wenfeng Tan, Fan Liu, Xionghan Feng","doi":"10.1186/s12932-018-0058-3","DOIUrl":"https://doi.org/10.1186/s12932-018-0058-3","url":null,"abstract":"<p>Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O<sub>2</sub> as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~?pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O<sub>2</sub> back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0058-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4862706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Regional geochemical baseline concentration of potentially toxic trace metals in the mineralized Lom Basin, East Cameroon: a tool for contamination assessment","authors":"Mumbfu Ernestine Mimba, Takeshi Ohba, Salomon César Nguemhe Fils, Melvin Tamnta Nforba, Nozomi Numanami, Tasin Godlove Bafon, Festus Tongwa Aka, Cheo Emmanuel Suh","doi":"10.1186/s12932-018-0056-5","DOIUrl":"https://doi.org/10.1186/s12932-018-0056-5","url":null,"abstract":"<p>The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (<?150?μm) was subjected to total digestion (HClO<sub>4</sub>?+?HF?+?HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39–86%), phyllosilicates (0–45%) and feldspars (0–27%). Mean concentrations of the analyzed metals are low (e.g. As?=?99.40?μg/kg, Zn?=?573.24?μg/kg, V?=?963.14?μg/kg and Cr?=?763.93?μg/kg). Iron and Mn have significant average concentrations of 28.325 and 442?mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni–Cr–V–Co–As–Se–pH, Cu–Zn–Hg–Pb–Cd–Sc and Fe–Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co–Cr–V–Ni and Cu–Zn–Pb–Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0056-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4095228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Review of interactions between phosphorus and arsenic in soils from four case studies","authors":"Daniel G. Strawn","doi":"10.1186/s12932-018-0055-6","DOIUrl":"https://doi.org/10.1186/s12932-018-0055-6","url":null,"abstract":"<p>Arsenic is a non-essential element that poses risks in many environments, including soil, groundwater, and surface water. Insights into the environmental biogeochemistry of As can be gained by comparing As and P reaction processes. Arsenic and P are chemical analogues, and it is proposed that they have similar chemical behaviors in environmental systems. However some chemical properties of As and P are distinct, such as redox reactions, causing the biogeochemical behavior of the two elements to differ. In the environment, As occurs as either As(V) or As(III) oxyanions (e.g., AsO<sub>4</sub><sup>3?</sup> or AsO<sub>3</sub><sup>3?</sup>). In contrast, P occurs predominantly as oxidation state five plus; most commonly as the orthophosphate ion (PO<sub>4</sub><sup>3?</sup>). In this paper, data from four published case studies are presented with a focus on P and As distribution and speciation in soil. The goal is show how analyzing P chemistry in soils can provide greater insights into As reaction processes in soils. The case studies discussed include: (1) soil developed from shale parent material, (2) mine-waste impacted wetland soils, (3) phosphate-amended contaminated soil, and (4) plants grown in biochar-amended, mine-contaminated soil. Data show that while P and As have competitive reactions in soils, in most natural systems they have distinct biogeochemical processes that create differing mobility and bioavailability. These processes include redox reactions and rhizosphere processes that affect As bioavailability. Results from these case studies are used as examples to illustrate how studying P and As together allows for enhanced interpretation of As biogeochemical processes in soils.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0055-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4064646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wenxian Gou, Matthew G. Siebecker, Zimeng Wang, Wei Li
{"title":"Competitive sorption of Ni and Zn at the aluminum oxide/water interface: an XAFS study","authors":"Wenxian Gou, Matthew G. Siebecker, Zimeng Wang, Wei Li","doi":"10.1186/s12932-018-0054-7","DOIUrl":"https://doi.org/10.1186/s12932-018-0054-7","url":null,"abstract":"<p>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-Al<sub>2</sub>O<sub>3</sub>) 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-Al<sub>2</sub>O<sub>3</sub>. 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.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0054-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5054784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}