Geochemical Transactions最新文献

{"title":"Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms","authors":"Sylvain Grangeon,&nbsp;Alejandro Fernandez-Martinez,&nbsp;Fabienne Warmont,&nbsp;Alexandre Gloter,&nbsp;Nicolas Marty,&nbsp;Agnieszka Poulain,&nbsp;Bruno Lanson","doi":"10.1186/s12932-015-0028-y","DOIUrl":"https://doi.org/10.1186/s12932-015-0028-y","url":null,"abstract":"<p>Vernadite is a nanocrystalline and turbostratic phyllomanganate which is ubiquitous in the environment. Its layers are built of (MnO₆)^8? octahedra connected through their edges and frequently contain vacancies and? (or) isomorphic substitutions. Both create a layer charge deficit that can exceed 1 valence unit per layer octahedron and thus induces a strong chemical reactivity. In addition, vernadite has a high affinity for many trace elements (e.g., Co, Ni, and Zn) and possesses a redox potential that allows for the oxidation of redox-sensitive elements (e.g., As, Cr, Tl). As a result, vernadite acts as a sink for many trace metal elements. In the environment, vernadite is often found associated with tectomanganates (e.g., todorokite and cryptomelane) of which it is thought to be the precursor. The transformation mechanism is not yet fully understood however and the fate of metals initially contained in vernadite structure during this transformation is still debated. In the present work, the transformation of synthetic vernadite (δ-MnO₂) to synthetic cryptomelane under conditions analogous to those prevailing in soils (dry state, room temperature and ambient pressure, in the dark) and over a time scale of ~10?years was monitored using high-energy X-ray scattering (with both Bragg-rod and pair distribution function formalisms) and transmission electron microscopy.</p><p>Migration of Mn³⁺ from layer to interlayer to release strains and their subsequent sorption above newly formed vacancy in a triple-corner sharing configuration initiate the reaction. Reaction proceeds with preferential growth to form needle-like crystals that subsequently aggregate. Finally, the resulting lath-shaped crystals stack, with <i>n</i>?×?120° (<i>n</i>?=?1 or 2) rotations between crystals. Resulting cryptomelane crystal sizes are ~50–150?nm in the <b>ab</b> plane and ~10–50?nm along <b>c*</b>, that is a tenfold increase compared to fresh samples.</p><p>The presently observed transformation mechanism is analogous to that observed in other studies that used higher temperatures and (or) pressure, and resulting tectomanganate crystals have a number of morphological characteristics similar to natural ones. This pleads for the relevance of the proposed mechanism to environmental conditions.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0028-y","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4105564","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":"Aerobic and anaerobic reduction of birnessite by a novel Dietzia strain","authors":"Huiqin Zhang,&nbsp;Yan Li,&nbsp;Xin Wang,&nbsp;Anhuai Lu,&nbsp;Hongrui Ding,&nbsp;Cuiping Zeng,&nbsp;Xiao Wang,&nbsp;Xiaolei Wu,&nbsp;Yong Nie,&nbsp;Changqiu Wang","doi":"10.1186/s12932-015-0026-0","DOIUrl":"https://doi.org/10.1186/s12932-015-0026-0","url":null,"abstract":"<p>Mn oxides occur in a wide variety of geological settings and exert considerable influences on the components and chemical behaviors of sediments and soils. Microbial reduction of Mn oxides is an important process found in many different environments including marine and freshwater sediments, lakes, anoxic basins, as well as oxic-anoxic transition zone of ocean. Although the pathway of Mn anaerobic reduction by two model bacteria, <i>Geobacter</i> and <i>Shewanella</i>, has been intensively studied, Mn bio-reduction is still the least well-explored process in nature. Particularly, reduction of Mn oxides by other bacteria and in the presence of O₂ has been fewly reported in recent publishes.</p><p>A series of experiments were conducted to understand the capability of <i>Dietzia</i> DQ12-45-1b in bioreduction of birnessite. In anaerobic systems, Mn reduction rate reached as high as 93% within 4?weeks when inoculated with 1.0?×?10¹⁰ cells/mL <i>Dietzia</i> DQ12-45-1b strains. Addition of AQDS enhanced Mn reduction rate from 53 to 91%. The anaerobic reduction of Mn was not coupled by any increase in bacterial protein concentration, and the reduction rate in the stable stage of day 2–14 was found to be in good proportion to the protein concentration. The anaerobic reduction of birnessite released Mn(II) either into the medium or adsorbed on the mineral or bacteria surface and resulted in the dissolution of birnessite as indicated by XRD, SEM and XANES. Under aerobic condition, the reduction rate was only 37% with a cell concentration of 1.0?×?10¹⁰ cells/mL, much lower than that in parallel anaerobic treatment. Bacterial growth under aerobic condition was indicated by time-course increase of protein and pH. In contrast to anaerobic experiments, addition of AQDS decreased Mn reduction rate from 25 to 6%. The reduced Mn(II) combined with carbon dioxide produced by acetate metabolism, as well as an alkaline pH environment given by cell growth, finally resulted in the formation of Mn(II)-bearing carbonate (kutnohorite), which was verified by XRD and XANES results. The system with the highest cell concentration of 1.0?×?10¹⁰ cells/mL gave rise to the most amount of kutnohorite, while concentration of Mn(II) produced with cell concentration of 6.2?×?10⁸ cells/mL was too low to thermodynamically favor the formation of kutnohorite but result in the formation of aragonite instead.</p><p>\u0000 <i>Dietzia</i> DQ12-45-1b was able to anaerobically and aerobically reduce birnessite. The rate and extent of Mn(IV) reduction depend on cell concentration, addition of AQDS or not, and presence of O₂ or not. Meanwhile, Mn(IV) bioreduction extent and suspension conditions determined the insoluble mineral products.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0026-0","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4331323","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":"Decolorization of RhB dye by manganese oxides: effect of crystal type and solution pH","authors":"Hao-Jie Cui,&nbsp;Hai-Zheng Huang,&nbsp;Baoling Yuan,&nbsp;Ming-Lai Fu","doi":"10.1186/s12932-015-0024-2","DOIUrl":"https://doi.org/10.1186/s12932-015-0024-2","url":null,"abstract":"<p>Organic dye pollution in water has become a major source of environmental pollution. Mn(III/IV) oxides \u0000have attracted a great deal of attention to remove organic dye pollutants due to their unique structures and physicochemical properties. Numerous studies have reported the removal of dye by various Mn(III/IV) oxides through catalytic degradation and adsorption. The crystalline structures of manganese oxides and solution pH may exert substantial impact on the removal of dyes. However, few studies have focused on the oxidative degradation of RhB dye using Mn(III/IV) oxides with different crystal structures during a spontaneous reaction. In the present study, three manganese oxides with different crystal type (α-MnO₂, β-MnO₂, and δ-MnO₂) were prepared by refluxing process to decolorize RhB dye in various pH solutions.</p><p>The results showed that the decolorization efficiencies of RhB for the three manganese oxides all increase with decrease solution pH. α-MnO₂ exhibited highest activity and could efficiently degrade RhB at pH 2–6. The degradation of RhB by β-MnO₂ and δ-MnO₂ could be observed at pH 2–3, and only little adsorption RhB on manganese oxides could be found at pH 4–6. The UPLC/MS analysis suggests that the decolorization of RhB by manganese oxides consists of three main stages: (1) cleavage of the ethyl groups from RhB molecular to form Rh; (2) further destruction of –COOH and –CNH₂ from Rh to form the small molecular substances; (3) mineralization of the small molecular substances into CO₂, H₂O, NO₃\u0000 ^? and NH₄\u0000 ⁺.</p><p>Overall, these results indicate that α-MnO₂ may be envisaged as efficient oxidants for the treatment of organic dye-containing wastewater under acid conditions.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0024-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5342803","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":"Characterization, dissolution and solubility of synthetic cadmium hydroxylapatite [Cd5(PO4)3OH] at 25–45°C","authors":"Yinian Zhu,&nbsp;Zongqiang Zhu,&nbsp;Xin Zhao,&nbsp;Yanpeng Liang,&nbsp;Liuqin Dai,&nbsp;Yanhua Huang","doi":"10.1186/s12932-015-0025-1","DOIUrl":"https://doi.org/10.1186/s12932-015-0025-1","url":null,"abstract":"&lt;p&gt;The substitution of Ca&lt;sup&gt;2+&lt;/sup&gt; in Ca-hydroxylapatite by toxic Cd&lt;sup&gt;2+&lt;/sup&gt; can cause the forming of Cd-hydroxylapatite and is a significant issue in a great variety of research areas, which hence needs an understanding of the essential physicochemical characteristics. Unfortunately, the solubility product and thermodynamic data for Cd-hydroxylapatite in water under a variety of conditions now are lacking. Little information has been reported by previous researchers. Additionally, the dissolution mechanism of Cd-hydroxylapatite has never been studied.&lt;/p&gt;&lt;p&gt;Dissolution of the synthetic cadmium hydroxylapatite [Cd-HAP, Cd&lt;sub&gt;5&lt;/sub&gt;(PO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;OH] in HNO&lt;sub&gt;3&lt;/sub&gt; solution (pH?=?2), ultrapure water (pH?=?5.6) and NaOH solution (pH?=?9) was experimentally studied at 25, 35 and 45°C. Characterization by XRD, FT-IR and FE-SEM proved that Cd-HAP solids showed no recognizable change during dissolution. For the Cd-HAP dissolution in aqueous acidic media at initial pH 2 and 25°C, the solution cadmium and phosphate concentrations increased rapidly and reached the peak values after 20–30?days and 10?days reaction, respectively. Thereafter, the Cd-HAP dissolution rate decreased slowly, whereas the solution Cd/P molar ratio increased constantly from 1.65–1.69 to 6.61–6.76. The mean &lt;i&gt;K&lt;/i&gt;\u0000 &lt;sub&gt;sp&lt;/sub&gt; values for Cd&lt;sub&gt;5&lt;/sub&gt;(PO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;OH were determined to be 10&lt;sup&gt;?64.62&lt;/sup&gt; (10&lt;sup&gt;?64.53&lt;/sup&gt;–10&lt;sup&gt;?64.71&lt;/sup&gt;) at 25°C, 10&lt;sup&gt;?65.58&lt;/sup&gt; (10&lt;sup&gt;?65.31&lt;/sup&gt;–10&lt;sup&gt;?65.80&lt;/sup&gt;) at 35°C and 10&lt;sup&gt;?66.57&lt;/sup&gt; (10&lt;sup&gt;?66.24&lt;/sup&gt;–10&lt;sup&gt;?66.90&lt;/sup&gt;) at 45°C. Based on the obtained solubility data from the dissolution at initial pH 2 and 25°C, the Gibbs free energy of Cd&lt;sub&gt;5&lt;/sub&gt;(PO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;OH forming &lt;span&gt;(Delta G_{f}^{o})&lt;/span&gt; was determined to be ?3,970.47?kJ/mol (?3,969.92 to ?3,970.96?kJ/mol). Thermodynamic parameters, Δ&lt;i&gt;G&lt;/i&gt;\u0000 &lt;sup&gt;0&lt;/sup&gt;, Δ&lt;i&gt;H&lt;/i&gt;\u0000 &lt;sup&gt;0&lt;/sup&gt;, Δ&lt;i&gt;S&lt;/i&gt;\u0000 &lt;sup&gt;0&lt;/sup&gt;, and &lt;span&gt;(Delta C_{text{p}}^{ 0})&lt;/span&gt; for the dissolution process of Cd-HAP in aqueous acidic media at initial pH 2 and 25°C were calculated 368,710.12?J/K?mol, ?158,809.54?J/mol, ?1,770.20 and ?869.53?J/K?mol, respectively.&lt;/p&gt;&lt;p&gt;Based on the experimental results of the present work and some previous researches, the cadmium hydroxylapatite (Cd-HAP) dissolution in aqueous media is considered to have the following coincident processes: the stoichiometric dissolution coupled with protonation and complexation reactions, the non-stoichiometric dissolution with Cd&lt;sup&gt;2+&lt;/sup&gt; release and PO&lt;sub&gt;4&lt;/sub&gt;\u0000 &lt;sup&gt;3?&lt;/sup&gt; sorption and the sorption of Cd&lt;sup&gt;2+&lt;/sup&gt; and PO&lt;sub&gt;4&lt;/sub&gt;\u0000 &lt;sup&gt;3?&lt;/sup&gt; species from solution backwards onto Cd-HAP surface. The obtained solubility products (&lt;i&gt;K&lt;/i&gt;\u0000 &lt;sub&gt;sp&lt;/sub&gt;","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0025-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4719724","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":"Formation of todorokite from “c-disordered” H+-birnessites: the roles of average manganese oxidation state and interlayer cations","authors":"Huaiyan Zhao,&nbsp;Xinran Liang,&nbsp;Hui Yin,&nbsp;Fan Liu,&nbsp;Wenfeng Tan,&nbsp;Guohong Qiu,&nbsp;Xionghan Feng","doi":"10.1186/s12932-015-0023-3","DOIUrl":"https://doi.org/10.1186/s12932-015-0023-3","url":null,"abstract":"<p>Todorokite, a 3?×?3 tectomanganate, is one of three main manganese oxide minerals in marine nodules and can be used as an active MnO₆ octahedral molecular sieve. The formation of todorokite is closely associated with the poorly crystalline phyllomanganates in nature. However, the effect of the preparative parameters on the transformation of “<i>c</i>-disordered” H⁺-birnessites, analogue to natural phyllomanganates, into todorokite has not yet been explored.</p><p>Synthesis of “<i>c</i>-disordered” H⁺-birnessites with different average manganese oxidation states (AOS) was performed by controlling the MnO₄\u0000 ^?/Mn²⁺ ratio in low-concentrated NaOH or KOH media. Further transformation to todorokite, using “<i>c</i>-disordered” H⁺-birnessites pre-exchanged with Na⁺ or K⁺ or not before exchange with Mg²⁺, was conducted under reflux conditions to investigate the effects of Mn AOS and interlayer cations. The results show that all of these “<i>c</i>-disordered” H⁺-birnessites exhibit hexagonal layer symmetry and can be transformed into todorokite to different extents. “<i>c</i>-disordered” H⁺-birnessite without pre-exchange treatment contains lower levels of Na/K and is preferably transformed into ramsdellite with a smaller 1?×?2 tunnel structure rather than todorokite. Na⁺ pre-exchange, i.e. to form Na-H-birnessite, greatly enhances transformation into todorokite, whereas K⁺ pre-exchange, i.e. to form K-H-birnessite, inhibits the transformation. This is because the interlayer K⁺ of birnessite cannot be completely exchanged with Mg²⁺, which restrains the formation of tunnel “walls” with 1?nm in length. When the Mn AOS values of Na-H-birnessite increase from 3.58 to 3.74, the rate and extent of the transformation sharply decrease, indicating that a key process is Mn(III) species migration from layer into interlayer to form the tunnel structure during todorokite formation.</p><p>Structural Mn(III), together with the content and type of interlayer metal ions, plays a crucial role in the transformation of “<i>c</i>-disordered” H⁺-birnessites with hexagonal symmetry into todorokite. This provides further explanation for the common occurrence of todorokite in the hydrothermal ocean environment, where is usually enriched in large metal ions such as Mg, Ca, Ni, Co and etc. These results have significant implications for exploring the origin and formation process of todorokite in various geochemical settings and promoting the practical application of todorokite in many fields.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0023-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4607412","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":"Annual sulfur cycle in a warm monomictic lake with sub-millimolar sulfate concentrations","authors":"Nadav Knossow,&nbsp;Barak Blonder,&nbsp;Werner Eckert,&nbsp;Alexandra V Turchyn,&nbsp;Gilad Antler,&nbsp;Alexey Kamyshny Jr.","doi":"10.1186/s12932-015-0021-5","DOIUrl":"https://doi.org/10.1186/s12932-015-0021-5","url":null,"abstract":"<p>We studied the annual variability of the concentration and isotopic composition of main sulfur species and sulfide oxidation intermediates in the water column of monomictic fresh-water Lake Kinneret. Sulfate concentrations in the lake are &lt;1?mM and similar to concentrations that are proposed to have existed in the Paleoproterozoic ocean. The main goal of this research was to explore biogeochemical constrains of sulfur cycling in the modern low-sulfate fresh-water lake and to identify which processes may be responsible for the isotopic composition of sulfur species in the Precambrian sedimentary rocks.</p><p>At the deepest point of the lake, the sulfate inventory decreases by more than 20% between March and December due to microbial sulfate reduction leading to the buildup of hydrogen sulfide. During the initial stages of stratification, sulfur isotope fractionation between sulfate and hydrogen sulfide is low (11.6?‰) and sulfur oxyanions (e.g. thiosulfate and sulfite) are the main products of the incomplete oxidation of hydrogen sulfide. During the stratification and at the beginning of the lake mixing (July–December), the inventory of hydrogen sulfide as well as of sulfide oxidation intermediates in the water column increases and is accompanied by an increase in sulfur isotope fractionation to 30?±?4?‰ in October. During the period of erosion of the chemocline, zero-valent sulfur prevails over sulfur oxyanions. In the terminal period of the mixing of the water column (January), the concentration of hydrogen sulfide decreases, the inventory of sulfide oxidation intermediates increases, and sulfur isotope fractionation decreases to 20?±?2?‰.</p><p>Sulfide oxidation intermediates are present in the water column of Lake Kinneret at all stages of stratification with significant increase during the mixing of the water column. Hydrogen sulfide inventory in the water column increases from March to December, and sharply decreases during the lake mixis in January. Sulfur isotope fractionation between sulfate and hydrogen sulfide as well as concentrations of sulfide oxidation intermediates can be explained either by microbial sulfate reduction alone or by microbial sulfate reduction combined with microbial disproportionation of sulfide oxidation intermediates. Our study of sulfur cycle in Lake Kinneret may be useful for understanding the range of biogeochemical processes in low sulfate oceans over Earth history.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0021-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4085558","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":"Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale","authors":"Clinton W Noack,&nbsp;Jinesh C Jain,&nbsp;John Stegmeier,&nbsp;J Alexandra Hakala,&nbsp;Athanasios K Karamalidis","doi":"10.1186/s12932-015-0022-4","DOIUrl":"https://doi.org/10.1186/s12932-015-0022-4","url":null,"abstract":"<p>In this work, the geochemistry of the rare earth elements (REE) was studied in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0022-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5012065","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":"Absorption mechanisms of Cu2+ on a biogenic bixbyite-like Mn2O3 produced by Bacillus CUA isolated from soil","authors":"Zhijun Zhang,&nbsp;Jing Lai,&nbsp;Hui Yin,&nbsp;Xionghan Feng,&nbsp;Wenfeng Tan,&nbsp;Fan Liu","doi":"10.1186/s12932-015-0020-6","DOIUrl":"https://doi.org/10.1186/s12932-015-0020-6","url":null,"abstract":"<p>Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. However, sorption characteristics and underlying mechanisms of the adsorption of heavy-metal ions on these biogenic Mn oxides are still rarely addressed. In this study, the sorption mechanisms of Cu(II) on a low valence biogenic Mn oxide, poorly crystallized bixbyite-like Mn₂O₃ (α-Mn₂O₃), were investigated.</p><p>The maximum adsorption capacity of Cu(II) onto this biogenic Mn oxide at pH?6.00 was 796?mmol/kg (0.45?mol Cu mol^?1 Mn). The complex structure of adsorbed Cu(II) was constrained using Cu extended X-ray absorption fine structure (EXAFS) analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO₆ octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. The sorbed Cu(II) was found to coordinate with the biogenic Mn oxide particle edges as inner-sphere complexes. At a relatively low Cu²⁺ loading (233?mmol/kg, pH?6.00), Cu(II) adsorbed onto the biogenic Mn oxide with two types of coordinated complexes, i.e., (1) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex and (2) with two adjacent MnO₆ octahedra as a bidentate-binuclear complex. While, at a relatively high Cu²⁺ loading (787?mmol/kg, pH?6.00), only one type of coordinated complex was constrained, the adsorbed Cu(II) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex.</p><p>This research extends further insight into the bacterial Mn(II) oxidation in the environment and serves as a good reference for understanding the interactions between metal ions and biogenic low valence Mn oxides, which are still poorly explored either theoretically or practically.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0020-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4547984","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":"Biomineralisation by earthworms – an investigation into the stability and distribution of amorphous calcium carbonate","authors":"Mark E Hodson,&nbsp;Liane G Benning,&nbsp;Bea Demarchi,&nbsp;Kirsty E H Penkman,&nbsp;Juan D Rodriguez-Blanco,&nbsp;Paul F Schofield,&nbsp;Emma A A Versteegh","doi":"10.1186/s12932-015-0019-z","DOIUrl":"https://doi.org/10.1186/s12932-015-0019-z","url":null,"abstract":"<p>Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis.</p><p>The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg^?1 (n = 3; ± std dev) per individual amino acid); the CaCO₃ phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν₂: ν₄ peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA.</p><p>ACC present in earthworm CaCO₃ granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0019-z","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5516344","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":"Zn isotope fractionation in a pristine larch forest on permafrost-dominated soils in Central Siberia","authors":"Jerome Viers,&nbsp;Anatoly S Prokushkin,&nbsp;Oleg S Pokrovsky,&nbsp;Alexander V Kirdyanov,&nbsp;Cyril Zouiten,&nbsp;Jerome Chmeleff,&nbsp;Merlin Meheut,&nbsp;Francois Chabaux,&nbsp;Priscia Oliva,&nbsp;Bernard Dupré","doi":"10.1186/s12932-015-0018-0","DOIUrl":"https://doi.org/10.1186/s12932-015-0018-0","url":null,"abstract":"<p>Stable Zn isotopes fractionation was studied in main biogeochemical compartments of a pristine larch forest of Central Siberia developed over continuous permafrost basalt rocks. Two north- and south-oriented watershed slopes having distinctly different vegetation biomass and active layer depth were used as natural proxy for predicting possible future climate changes occurring in this region. In addition, peat bog zone exhibiting totally different vegetation, hydrology and soil temperature regime has been studied.</p><p>The isotopic composition of soil profile from Central Siberia is rather constant with a δ⁶⁶Zn value around 0.2‰ close to the value of various basalts. Zn isotopic composition in mosses (<i>Sphagnum fuscum and Pleurozium schreberi</i>) exhibits differences between surface layers presenting values from 0.14 to 0.2‰ and bottom layers presenting significantly higher values (0.5 – 0.7‰) than the underlain mineral surface. The humification of both dead moss and larch needles leads to retain the fraction where Zn bound most strongly thus releasing the lighter isotopes in solution and preserving the heavy isotopes in the humification products, in general accord with previous experimental and modeling works [GCA 75:7632–7643, 2011].</p><p>The larch <i>(Larix gmelinii</i>) from North and South-facing slopes is enriched in heavy isotopes compared to soil reservoir while larch from Sphagnum peatbog is enriched in light isotopes. This difference may result from stronger complexation of Zn by organic ligands and humification products in the peat bog compared to mineral surfaces in North- and South-facing slope.</p><p>During the course of the growing period, Zn followed the behavior of macronutrients with a decrease of concentration from June to September. During this period, an enrichment of larch needles by heavier Zn isotopes is observed in the various habitats. We suggest that the increase of the depth of rooting zone, and the decrease of DOC and Zn concentration in soil solution from the root uptake zone with progressively thawing soil could provoke heavy isotopes to become more available for the larch roots at the end of the vegetative season compared to the beginning of the season, because the decrease of DOC will facilitate the uptake of heavy isotope as it will be less retained in strong organic complexes.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"16 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2015-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-015-0018-0","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4633588","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}