Geochemical Transactions最新文献

{"title":"The synergistic effect of calcium on organic carbon sequestration to ferrihydrite","authors":"Tyler D. Sowers,&nbsp;Jason W. Stuckey,&nbsp;Donald L. Sparks","doi":"10.1186/s12932-018-0049-4","DOIUrl":"https://doi.org/10.1186/s12932-018-0049-4","url":null,"abstract":"<p>Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca²⁺) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca²⁺ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca²⁺ increased across all tested pH values, especially at pH ≥?7. Sorbed OC concentration at pH 9 increased from 8.72?±?0.16 to 13.3?±?0.20?mmol OC g^?1 ferrihydrite between treatments of no added Ca²⁺ and 30?mM Ca²⁺ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0049-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4115723","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":"Effects of humic substances on Fe(II) sorption onto aluminum oxide and clay","authors":"Ying Zhu,&nbsp;Jingjing Liu,&nbsp;Omanjana Goswami,&nbsp;Ashaki A. Rouff,&nbsp;Evert J. Elzinga","doi":"10.1186/s12932-018-0048-5","DOIUrl":"https://doi.org/10.1186/s12932-018-0048-5","url":null,"abstract":"<p>We studied the effects of humic substances (HS) on the sorption of Fe(II) onto Al-oxide and clay sorbents at pH 7.5 with a combination of batch kinetic experiments and synchrotron Fe <i>K</i>-edge EXAFS analyses. Fe(II) sorption was monitored over the course of 4?months in anoxic clay and Al-oxide suspensions amended with variable HS types (humic acid, HA; or fulvic acid, FA) and levels (0, 1, and 4 wt%), and with differing Fe(II) and HS addition sequences (co-sorption and pre-coated experiments, where Fe(II) sorbate was added alongside and after HS addition, respectively). In the Al-oxide suspensions, the presence of HS slowed down the kinetics of Fe(II) sorption, but had limited, if any, effect on the equilibrium aqueous Fe(II) concentrations. EXAFS analyses revealed precipitation of Fe(II)–Al(III)-layered double hydroxide (LDH) phases as the main mode of Fe(II) sorption in both the HA-containing and HA-free systems. These results demonstrate that HS slow down Fe(II) precipitation in the Al-oxide suspensions, but do not affect the composition or stability of the secondary Fe(II)–Al(III)-LDH phases formed. Interference of HS with the precipitation of Fe(II)–Al(III)-LDH was attributed to the formation organo-Al complexes HS limiting the availability of Al for incorporation into secondary layered Fe(II)-hydroxides. In the clay systems, the presence of HA caused a change in the main Fe(II) sorption product from Fe(II)–Al(III)-LDH to a Fe(II)-phyllosilicate containing little structural Al. This was attributed to complexation of Al by HA, in combination with the presence of dissolved Si in the clay suspension enabling phyllosilicate precipitation. The change in Fe(II) precipitation mechanism did not affect the rate of Fe(II) sorption at the lower HA level, suggesting that the inhibition of Fe(II)–Al(III)-LDH formation in this system was countered by enhanced Fe(II)-phyllosilicate precipitation. Reduced rates of Fe(II) sorption at the higher HA level were attributed to surface masking or poisoning by HA of secondary Fe(II) mineral growth at or near the clay surface. Our results suggest that HS play an important role in controlling the kinetics and products of Fe(II) precipitation in reducing soils, with effects modulated by soil mineralogy, HS content, and HS properties. Further work is needed to assess the importance of layered Fe(II) hydroxides in natural reducing environments.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-018-0048-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4965995","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":"A geochemical view into continental palaeotemperatures of the end-Permian using oxygen and hydrogen isotope composition of secondary silica in chert rubble breccia: Kaibab Formation, Grand Canyon (USA)","authors":"Ray Kenny","doi":"10.1186/s12932-017-0047-y","DOIUrl":"https://doi.org/10.1186/s12932-017-0047-y","url":null,"abstract":"<p>The upper carbonate member of the Kaibab Formation in northern Arizona (USA) was subaerially exposed during the end Permian and contains fractured and zoned chert rubble lag deposits typical of karst topography. The karst chert rubble has secondary (authigenic) silica precipitates suitable for estimating continental weathering temperatures during the end Permian karst event. New oxygen and hydrogen isotope ratios of secondary silica precipitates in the residual rubble breccia: (1) yield continental palaeotemperature estimates between 17 and 22?°C; and, (2) indicate that meteoric water played a role in the crystallization history of the secondary silica. The continental palaeotemperatures presented herein are broadly consistent with a global mean temperature estimate of 18.2?°C for the latest Permian derived from published climate system models. Few data sets are presently available that allow even approximate quantitative estimates of regional continental palaeotemperatures. These data provide a basis for better understanding the end Permian palaeoclimate at a seasonally-tropical latitude along the western shoreline of Pangaea.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0047-y","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4645751","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":"Chemical speciation and fate of tripolyphosphate after application to a calcareous soil","authors":"Jordan G. Hamilton,&nbsp;Jay Grosskleg,&nbsp;David Hilger,&nbsp;Kris Bradshaw,&nbsp;Trevor Carlson,&nbsp;Steven D. Siciliano,&nbsp;Derek Peak","doi":"10.1186/s12932-017-0046-z","DOIUrl":"https://doi.org/10.1186/s12932-017-0046-z","url":null,"abstract":"<p>Adsorption and precipitation reactions often dictate the availability of phosphorus in soil environments. Tripolyphosphate (TPP) is considered a form of slow release P fertilizer in P limited soils, however, investigations of the chemical fate of TPP in soils are limited. It has been proposed that TPP rapidly hydrolyzes in the soil solution before adsorbing or precipitating with soil surfaces, but in model systems, TPP also adsorbs rapidly onto mineral surfaces. To study the adsorption behavior of TPP in calcareous soils, a short-term (48?h) TPP spike was performed under laboratory conditions. To determine the fate of TPP under field conditions, two different liquid TPP amendments were applied to a P limited subsurface field site via an in-ground injection system. Phosphorus speciation was assessed using X-ray absorption spectroscopy, total and labile extractable P, and X-ray diffraction. Adsorption of TPP to soil mineral surfaces was rapid (&lt;?48?h) and persisted without fully hydrolyzing to ortho-P. Linear combination fitting of XAS data indicated that the distribution of adsorbed P was highest (~?30–40%) throughout the site after the first TPP amendment application (high water volume and low TPP concentrations). In contrast, lower water volumes with more concentrated TPP resulted in lower relative fractions of adsorbed P (15–25%), but a significant increase in total P concentrations (~?3000?mg?P?kg?soil) and adsorbed P (60%) directly adjacent to the injection system. This demonstrates that TPP application increases the adsorbed P fraction of calcareous soils through rapid adsorption reactions with soil mineral surfaces.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"19 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2018-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0046-z","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4341076","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":"Fe(II) reduction of pyrolusite (β-MnO2) and secondary mineral evolution","authors":"Michael V. Schaefer,&nbsp;Robert M. Handler,&nbsp;Michelle M. Scherer","doi":"10.1186/s12932-017-0045-0","DOIUrl":"https://doi.org/10.1186/s12932-017-0045-0","url":null,"abstract":"<p>Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth’s crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO₂) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and ⁵⁷Fe M?ssbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3?mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with ⁵⁷Fe M?ssbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3?mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0045-0","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4201178","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":"Interactions between magnetite and humic substances: redox reactions and dissolution processes","authors":"Anneli Sundman,&nbsp;James M. Byrne,&nbsp;Iris Bauer,&nbsp;Nicolas Menguy,&nbsp;Andreas Kappler","doi":"10.1186/s12932-017-0044-1","DOIUrl":"https://doi.org/10.1186/s12932-017-0044-1","url":null,"abstract":"<p>Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe₃O₄) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500?nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0044-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4774629","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":"A potential nitrogen sink discovered in the oxygenated Chukchi Shelf waters of the Arctic","authors":"Jian Zeng,&nbsp;Min Chen,&nbsp;Minfang Zheng,&nbsp;Wangjiang Hu,&nbsp;Yusheng Qiu","doi":"10.1186/s12932-017-0043-2","DOIUrl":"https://doi.org/10.1186/s12932-017-0043-2","url":null,"abstract":"<p>The western Arctic Shelf has long been considered as an important sink of nitrogen because high primary productivity of the shelf water fuels active denitrification within the sediments, which has been recognized to account for all the nitrogen (N) removal of the Pacific water inflow. However, potentially high denitrifying activity was discovered within the oxygenated Chukchi Shelf water during our summer expedition. Based on ¹⁵N-isotope pairing incubations, we estimated denitrification rates ranging from 1.8?±?0.4 to 75.9?±?8.7?nmol?N₂ L^?1?h^?1. We find that the spatial pattern of denitrifying activity follows well with primary productivity, which supplies plentiful fresh organic matter, and there was a strong correlation between integrated denitrification and integrated primary productivity. Considering the active hydrodynamics over the Chukchi Shelf during summer, resuspension of benthic sediment coupled with particle-associated bacteria induces an active denitrification process in the oxic water column. We further extrapolate to the whole Chukchi Shelf and estimate an N removal flux from this cold Arctic shelf water to be 12.2 Tg-N?year^?1, which compensates for the difference between sediment cores incubation (~?3 Tg-N?year^?1) and geochemical estimation based on N deficit relative to phosphorous (~?16 Tg-N?year^?1). We infer that dynamic sediment resuspension combined with high biological productivity stimulates intensive denitrification in the water column, potentially creating a nitrogen sink over the shallow Arctic shelves that have previously been unrecognized.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0043-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4806233","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":"Salinization and arsenic contamination of surface water in southwest Bangladesh","authors":"John C. Ayers,&nbsp;Gregory George,&nbsp;David Fry,&nbsp;Laura Benneyworth,&nbsp;Carol Wilson,&nbsp;Leslie Auerbach,&nbsp;Kushal Roy,&nbsp;Md. Rezaul Karim,&nbsp;Farjana Akter,&nbsp;Steven Goodbred","doi":"10.1186/s12932-017-0042-3","DOIUrl":"https://doi.org/10.1186/s12932-017-0042-3","url":null,"abstract":"<p>To identify the causes of salinization and arsenic contamination of surface water on an embanked island (i.e., polder) in the tidal delta plain of SW Bangladesh we collected and analyzed water samples in the dry (May) and wet (October) seasons in 2012–2013. Samples were collected from rice paddies (wet season), saltwater ponds used for brine shrimp aquaculture (dry season), freshwater ponds and tidal channels (both wet and dry season), and rainwater collectors. Continuous measurements of salinity from March 2012 to February 2013 show that tidal channel water increases from ~0.15 ppt in the wet season up to ~20 ppt in the dry season. On the polder, surface water exceeds the World Health Organization drinking water guideline of 10?μg As/L in 78% of shrimp ponds and 27% of rice paddies, raising concerns that produced shrimp and rice could have unsafe levels of As. Drinking water sources also often have unsafe As levels, with 83% of tubewell and 43% of freshwater pond samples having &gt;10?μg As/L. Water compositions and field observations are consistent with shrimp pond water being sourced from tidal channels during the dry season, rather than the locally saline groundwater from tubewells. Irrigation water for rice paddies is also obtained from the tidal channels, but during the wet season when surface waters are fresh. Salts become concentrated in irrigation water through evaporation, with average salinity increasing from 0.43 ppt in the tidal channel source to 0.91 ppt in the rice paddies. Our observations suggest that the practice of seasonally alternating rice and shrimp farming in a field has a negligible effect on rice paddy water salinity. Also, shrimp ponds do not significantly affect the salinity of adjacent surface water bodies or subjacent groundwater because impermeable shallow surface deposits of silt and clay mostly isolate surface water bodies from each other and from the shallow groundwater aquifer. Bivariate plots of conservative element concentrations show that all surface water types lie on mixing lines between dry season tidal channel water and rainwater, i.e., all are related by varying degrees of salinization. High As concentrations in dry season tidal channel water and shrimp ponds likely result from groundwater exfiltration and upstream irrigation in the dry season. Arsenic is transferred from tidal channels to rice paddies through irrigation. Including groundwater samples from the same area (Ayers et al. in Geochem Trans 17:1–22, 2016), principal components analysis and correlation analysis reveal that salinization explains most variation in surface water compositions, whereas progressive reduction of buried surface water by dissolved organic carbon is responsible for the nonconservative behavior of S, Fe, and As and changes in Eh and alkalinity of groundwater.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0042-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4478518","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":"Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations","authors":"Ying Chen,&nbsp;Eric J. Bylaska,&nbsp;John H. Weare","doi":"10.1186/s12932-017-0040-5","DOIUrl":"https://doi.org/10.1186/s12932-017-0040-5","url":null,"abstract":"<p>Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96?+?Grimme, and PBE0) in the simulations of a (3?×?2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a?=?30??, FeOOH slab ~12?? thick, solvation layer ~18?? thick).</p><p>The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe³⁺ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe³⁺. The water molecules capping surface Fe³⁺ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe³⁺ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe³⁺ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe³⁺, those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe³⁺ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025?exchanges/ps) using a dissociative mechanism.</p><p>Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe–OH₂ distances in the DFT calculations it was proposed that the surface Fe³⁺ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0040-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5180548","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":"Global hydrogen reservoirs in basement and basins","authors":"John Parnell,&nbsp;Nigel Blamey","doi":"10.1186/s12932-017-0041-4","DOIUrl":"https://doi.org/10.1186/s12932-017-0041-4","url":null,"abstract":"<p>Hydrogen is known to occur in the groundwaters of some ancient cratons. Where associated gases have been dated, their age extends up to a billion years, and the hydrogen is assumed also to be very old. These observations are interpreted to represent the radiolysis of water and hydration reactions and migration of hydrogen into fracture systems. A hitherto untested implication is that the overwhelming bulk of the ancient low-permeability basement, which is not adjacent to cross-cutting fractures, constitutes a reservoir for hydrogen.</p><p>New data obtained from cold crushing to liberate volatiles from fluid inclusions confirm that granites and gneiss of Archean and Palaeoproterozoic (&gt;1600?Ma) age typically contain an order of magnitude greater hydrogen in their entrained fluid than very young (&lt;200?Ma) granites. Sedimentary rocks containing clasts of old basement also include a greater proportion of hydrogen than the young granites.</p><p>The data support the case for a global reservoir of hydrogen in both the ancient basement and in the extensive derived sediments. These reservoirs are susceptible to the release of hydrogen through a variety of mechanisms, including deformation, attrition to reduce grain size and diagenetic alteration, thereby contributing to the hydrogen required by chemolithoautotrophs in the deep biosphere.</p>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"18 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2017-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1186/s12932-017-0041-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4801315","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}