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Geochemical Transactions

Jason W Stuckey, Christopher Goodwin, Jian Wang, Louis A Kaplan, Prian Vidal-Esquivel, Thomas P Beebe, Donald L Sparks
Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides-collectively referred to as "oxides" hereafter-are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oahorizon leachate ("O horizon leachate" hereafter) than does goethite under acidic (pH 5) conditions...
February 13, 2018: Geochemical Transactions
Tingting Fan, Chengbao Li, Juan Gao, Dongmei Zhou, Marcelo Eduardo Alves, Yujun Wang
BACKGROUND: The coexistence of Cd2+ and Zn2+ ions in nature has a significant influence on their environmental behaviors in soils and bioavailability for plants. While many studies have been done on the mutual toxicity of Cd2+ and Zn2+, few studies can be found in the literature focused on the interaction of Cd2+ and Zn2+ on soil clay fractions especially in terms of energy relationship. RESULTS: The binding energies of Cd2+ on boggy soil (Histosols) particles and Zn2+ on yellow brown soil (Haplic Luvisols) particles were the highest, while those of Cd2+ and Zn2+ on paddy soil (Inceptisols) particles were the lowest...
February 13, 2018: Geochemical Transactions
Tyler D Sowers, Jason W Stuckey, Donald L Sparks
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...
February 3, 2018: Geochemical Transactions
Ying Zhu, Jingjing Liu, Omanjana Goswami, Ashaki A Rouff, Evert J Elzinga
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 K-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)...
January 25, 2018: Geochemical Transactions
Ray Kenny
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...
January 16, 2018: Geochemical Transactions
Jordan G Hamilton, Jay Grosskleg, David Hilger, Kris Bradshaw, Trevor Carlson, Steven D Siciliano, Derek Peak
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...
January 8, 2018: Geochemical Transactions
Michael V Schaefer, Robert M Handler, Michelle M Scherer
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 Mössbauer 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...
December 5, 2017: Geochemical Transactions
Anneli Sundman, James M Byrne, Iris Bauer, Nicolas Menguy, Andreas Kappler
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...
October 19, 2017: Geochemical Transactions
Jian Zeng, Min Chen, Minfang Zheng, Wangjiang Hu, Yusheng Qiu
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 (15)N-isotope pairing incubations, we estimated denitrification rates ranging from 1...
September 20, 2017: Geochemical Transactions
John C Ayers, Gregory George, David Fry, Laura Benneyworth, Carol Wilson, Leslie Auerbach, Kushal Roy, Md Rezaul Karim, Farjana Akter, Steven Goodbred
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...
September 11, 2017: Geochemical Transactions
Ying Chen, Eric J Bylaska, John H Weare
BACKGROUND: 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 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick)...
March 31, 2017: Geochemical Transactions
John Parnell, Nigel Blamey
BACKGROUND: 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...
March 20, 2017: Geochemical Transactions
Timothy A Doane
The participation of sunlight in the natural chemistry of the earth is presented as a unique field of study, from historical observations to prospects for future inquiry. A compilation of known reactions shows the extent of light-driven interactions between naturally occurring components of land, air, and water, and provides the backdrop for an outline of the mechanisms of these phenomena. Catalyzed reactions, uncatalyzed reactions, direct processes, and indirect processes all operate in natural photochemical transformations, many of which are analogous to well-known biological reactions...
2017: Geochemical Transactions
Samantha L Shumlas, Soujanya Singireddy, Akila C Thenuwara, Nuwan H Attanayake, Richard J Reeder, Daniel R Strongin
The effect of simulated solar radiation on the oxidation of arsenite [As(III)] to arsenate [As(V)] on the layered manganese oxide, birnessite, was investigated. Experiments were conducted where birnessite suspensions, under both anoxic and oxic conditions, were irradiated with simulated solar radiation in the presence of As(III) at pH 5, 7, and 9. X-ray absorption spectroscopy (XAS) was used to determine the nature of the adsorbed product on the surface of the birnessite. The oxidation of As(III) in the presence of birnessite under simulated solar light irradiation occurred at a rate that was faster than in the absence of light at pH 5...
2016: Geochemical Transactions
John C Ayers, Steven Goodbred, Gregory George, David Fry, Laura Benneyworth, George Hornberger, Kushal Roy, Md Rezaul Karim, Farjana Akter
BACKGROUND: High salinity and arsenic (As) concentrations in groundwater are widespread problems in the tidal deltaplain of southwest Bangladesh. To identify the sources of dissolved salts and As, groundwater samples from the regional shallow Holocene aquifer were collected from tubewells during the dry (May) and wet (October) seasons in 2012-2013. Thirteen drill cores were logged and 27 radiocarbon ages measured on wood fragments to characterize subsurface stratigraphy. RESULTS: Drill cuttings, exposures in pits and regional studies reveal a >5 m thick surface mud cap overlying a ~30 m thick upper unit of interbedded mud and fine sand layers, and a coarser lower unit up to 60 m thick dominated by clean sands, all with significant horizontal variation in bed continuity and thickness...
2016: Geochemical Transactions
Iván A Reyes, Ister Mireles, Francisco Patiño, Thangarasu Pandiyan, Mizraim U Flores, Elia G Palacios, Emmanuel J Gutiérrez, Martín Reyes
BACKGROUND: The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact...
2016: Geochemical Transactions
Yinian Zhu, Bin Huang, Zongqiang Zhu, Huili Liu, Yanhua Huang, Xin Zhao, Meina Liang
BACKGROUND: The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported...
2016: Geochemical Transactions
Amanda H Meena, Yuji Arai
BACKGROUND: Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (<a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems...
2016: Geochemical Transactions
Tianyu Gao, Yougang Shen, Zhaoheng Jia, Guohong Qiu, Fan Liu, Yashan Zhang, Xionghan Feng, Chongfa Cai
BACKGROUND: In soils and sediments, manganese oxides and oxygen usually participate in the oxidation of ferrous ions. There is limited information concerning the interaction process and mechanisms of ferrous ions and manganese oxides. The influence of air (oxygen) on reaction process and kinetics has been seldom studied. Because redox reactions usually occur in open systems, the participation of air needs to be further investigated. RESULTS: To simulate this process, hexagonal birnessite was prepared and used to oxidize ferrous ions in anoxic and aerobic aqueous systems...
December 2015: Geochemical Transactions
Rebecca B Chesne, Christopher S Kim
[This corrects the article DOI: 10.1186/1467-4866-15-6.].
2015: Geochemical Transactions
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