Geochemical Transactions最新文献

On Late Cretaceous Tethyan upwelling sediments from the Mishash/Ghareb Formation (Negev, Israel), bulk geochemical and biomarker analyses were performed to explain the high proportion of phosphates in the lower part and of organic matter (OM) preserved in upper parts of the studied section. The profile is composed of three facies types; the underlying Phosphate Member (PM), the Oil Shale Member (OSM) and the overlying Marl Member (MM).

Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.6% in the MM, to 24.5% in the OSM. Total iron (TFe) varies from 0.1% in the PM to 3.3% in the OSM. Total sulfur (TS) ranges between 0.1% in the MM and 3.4% in the OSM, resulting in a high C/S ratio of 6.5 in the OSM section. A mean proportion of 11.5% total phosphorus (TP) in the PM changed abruptly with the facies to a mean value of only 0.9% in the OSM and the MM.

The TOC/TOC_OR ratios argue for a high bacterial sulfate reduction activity and in addition, results from fatty acid analyses indicate that the activity of sulfide-oxidizing activity of bacteria was high during deposition of the PM, while decreasing during the deposition of the OSM.

The upwelling conditions effected a high primary productivity and consequently the presence of abundant OM. This, in combination with high sulfate availability in the sediments of the PM resulted in a higher sulfide production due to the activity of sulfate-reducing bacteria. Iron availability was a limiting factor during the deposition of the whole section, affecting the incorporation of S into OM. This resulted in the preservation of a substantial part of OM against microbial degradation due to naturally-occurring sulfurization processes expressed by the high C/S ratio of 6.5 in the OSM.

Further, the abundant sulfide in the pore water supported the growth of sulfide-oxidizing bacteria promoting the deposition of P, which amounted to as much as 15% in the PM. These conditions changed drastically from the PM to the OSM, resulting in a significant reduction of the apatite precipitation and a high concentration of reactive S species reacting with the OM.

Elemental sulfur (S) persists in natural aquatic environment in a variety of forms with different size distributions from dissolved to particulate. Determination of S speciation mainly consists of the application of chromatographic and electrochemical techniques while its size determination is limited only to the application of microscopic and light scattering techniques. S biological and geochemical importance together with recent increases of S industrial applications requires the development of different analytical tools for S sizing and quantification. In recent years the use of electrochemical measurements as a direct, fast, and inexpensive technique for the different nanoparticles (NPs) characterization (Ag, Au, Pt) is increasing. In this work, electrochemical i.e. chronoamperometric measurements at the Hg electrode are performed for determination of the size distribution of the S NPs.

S NPs were synthesized in aqueous medium by sodium polysulphide acidic hydrolysis. Chronoamperometric measurements reveal the polydisperse nature of the formed suspension of S NPs. The electrochemical results were compared with dynamic light scattering measurements parallel run in the same S NPs suspensions. The two methods show fairly good agreement, both suggesting a log-normal size distribution of the S NPs sizes characterized by similar parameters.

The preliminary results highlight the amperometric measurements as a promising tool for the size determination of the S NPs in the water environment.

Integrated Ocean Drilling Program Expedition 338 was the second scientific expedition with D/V Chikyu during which riser drilling was conducted as part of the Nankai Trough Seismogenic Zone Experiment. Riser drilling enabled sampling and real-time monitoring of drilling mud gas with an onboard scientific drilling mud gas monitoring system (“SciGas”). A second, independent system was provided by Geoservices, a commercial mud logging service. Both systems allowed the determination of (non-) hydrocarbon gas, while the SciGas system also monitored the methane carbon isotope ratio (δ¹³C_CH4). The hydrocarbon gas composition was predominated by methane (> 1%), while ethane and propane were up to two orders of magnitude lower. δ¹³C_CH4 values suggested an onset of thermogenic gas not earlier than 1600 meter below seafloor. This study aims on evaluating the onboard data and subsequent geological interpretations by conducting shorebased analyses of drilling mud gas samples.

During shipboard monitoring of drilling mud gas the SciGas and Geoservices systems recorded up to 8.64% and 16.4% methane, respectively. Ethane and propane concentrations reached up to 0.03 and 0.013%, respectively, in the SciGas system, but 0.09% and 0.23% in the Geoservices data. Shorebased analyses of discrete samples by gas chromatography showed a gas composition with ~0.01 to 1.04% methane, 2 – 18 ppmv ethane, and 2 – 4 ppmv propane. Quadruple mass spectrometry yielded similar results for methane (0.04 to 4.98%). With δD values between -171‰ and -164‰, the stable hydrogen isotopic composition of methane showed little downhole variability.

Although the two independent mud gas monitoring systems and shorebased analysis of discrete gas sample yielded different absolute concentrations they all agree well with respect to downhole variations of hydrocarbon gases. The data point to predominantly biogenic methane sources but suggest some contribution from thermogenic sources at depth, probably due to mixing. In situ thermogenic gas production at depths shallower 2000 mbsf is unlikely based on in situ temperature estimations between 81°C and 85°C and a cumulative time-temperature index of 0.23. In conclusion, the onboard SciGas data acquisition helps to provide a preliminary, qualitative evaluation of the gas composition, the in situ temperature and the possibility of gas migration.

The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 15-250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS).

Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface.

Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

Ionic and molecular carriers of dissolved (filter-passing) zero-valent sulfur (S⁰) in anaerobic natural waters include polysulfides, S_n^2?, molecular S₈(aq), organic macromolecules and certain higher valent thioanions. Because S⁰ is rapidly transferred among these various carriers, its biogeochemical roles in such processes as dehalogenation of organic compounds, chelation of trace metals, and anaerobic microbial metabolism are not determined solely by one ionic or molecular species. Here, S⁰ is treated collectively as a virtual thermodynamic component, and computational as well as graphical methods for quantifying its activity (a_S0) in natural waters are presented. From a_S0, concentrations of the ionic and molecular carriers of S⁰ can be calculated easily.

Concentration ratios of any two polysulfide ions define a_S0 (Method I). Unfortunately these concentrations are often too low in nature for accurate quantification with current methods. Measurements of total divalent sulfur (ΣS^-II), zero-valent sulfur (ΣS⁰) and pH provide a more widely applicable approach (Method II). Systematic errors in ΣS⁰ measurements are the main limit to accuracy of this method at the present time. Alternative methods based on greigite solubility and potentiometry are discussed. A critical comparison of Methods I and II reveals inconsistencies at low ΣS⁰/ΣS^-II that imply errors in the thermodynamic data for HS₂^? and S₂^?. For samples having low ΣS⁰/ΣS^-II, an interim remedy is recommended: letting pK_a2?=?6.3 for all HS_n^? ions.

Newly assembled data for a_S0 in a selection of anaerobic natural waters indicate that S⁰ is always metastable in the surveyed samples with respect to disproportionation to sulfide and sulfate. In all the surveyed environments, sulfur-rich minerals, such as greigite, covellite and orpiment, are stable in preference to their sulfur-poor cohorts, mackinawite, chalcocite and realgar. The a_S0 values in the dataset span conditions favoring Hg-polysulfide complexes vs. Hg-sulfide complexes, implying that a_S0 could affect Hg-methylation rates in nature. No support is found for the common assumption that a_S0?=?1 in reducing natural waters. This paper calls attention to an urgent need for improved measurement methods, especially for total zero-valent sulfur, as well as new determinations of ionization constants for all HS_n^? species.

Shallow-sea (5?m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1?m²) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H₂S) in the free gas had uniform δ³⁴S values (2.5?±?0.28‰, n?=?4) that were nearly identical to pore water H₂S (2.7?±?0.36‰, n?=?21). In pore water sulfate, there were no paired increases in δ³⁴S_SO4 and δ¹⁸O_SO4 as expected of microbial sulfate reduction. Instead, pore water δ³⁴S_SO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ³⁴S_SO4 as a mixing process between oxic seawater and ³⁴S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ³⁴S_SO4, the oxygen isotope composition of sulfate tended to be ¹⁸O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ¹⁸O_SO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H₂S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ³⁴S value of H₂S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H₂S-rich hydrothermal fluids and oxic, sulfate-rich seawater.

Pyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, the microbiological processes involved, and the effects of pyrite on human health. Elemental sulfur (S⁰) is a common product of incomplete pyrite oxidation. Preexisting S⁰ impurities as unaccounted reaction products are a source of experimental uncertainty, as are adhered fine grains of pyrite and its oxidation products. Removal of these impurities is, therefore, desirable.

A robust standardized pretreatment protocol for removal of fine particles and oxidation impurities from pyrite is lacking. Here we describe a protocol for S⁰ and fine particle removal from the surface of pyrite by rinsing in acid followed by repeated ultrasonication with warm acetone.

Our data demonstrate the presence of large fractions of S⁰ on untreated pyrite particle surfaces, of which only up to 60% was removed by a commonly used pretreatment method described by Moses et al. (GCA 51:1561-1571, 1987). In comparison, after pretreatment by the protocol proposed here, approximately 98% S⁰ removal efficiency was achieved. Additionally, the new procedure was more efficient at removal of fine particles of adhered pyrite and its oxidation products and did not appear to affect the particle size distribution, the specific surface area, or the properties of grain surfaces.

The suggested pyrite pretreatment protocol is more efficient in removal of impurities from pyrite grains, and provides multiple advantages for both kinetic and isotopic investigations of pyrite transformations under various environmental conditions.

Elemental sulfur exists is a variety of forms in natural systems, from dissolved forms (noted as S_8(diss) or in water as S_8(aq)) to bulk elemental sulfur (most stable as α-S₈). Elemental sulfur can form via several biotic and abiotic processes, many beginning with small sulfur oxide or polysulfidic sulfur molecules that coarsen into S₈ rings that then coalesce into larger forms:

Formation of elemental sulfur can be possible via two primary techniques to create an emulsion of liquid sulfur in water called sulfur sols that approximate some mechanisms of possible elemental sulfur formation in natural systems. These techniques produce hydrophobic (S_8(Weimarn)) and hydrophilic (S_{8(polysulfide)}) sols that exist as nanoparticle and colloidal suspensions. These sols begin as small sulfur oxide or polysulfidic sulfur molecules, or dissolved S_8(aq) forms, but quickly become nanoparticulate and coarsen into micron sized particles via a combination of classical nucleation, aggregation processes, and/or Ostwald ripening.

We conducted a series of experiments to study the rate of elemental sulfur particle coarsening using dynamic light scattering (DLS) analysis under different physical and chemical conditions. Rates of nucleation and initial coarsening occur over seconds to minutes at rates too fast to measure by DLS, with subsequent coarsening of S_8(nano) and S_8(sol) being strongly temperature dependent, with rates up to 20 times faster at 75°C compared to 20°C. The addition of surfactants (utilizing ionic and nonionic surfactants as model compounds) results in a significant reduction of coarsening rates, in addition to known effects of these molecules on elemental sulfur solubility. DLS and cryo-SEM results suggest coarsening is largely a product of ripening processes rather than particle aggregation, especially at higher temperatures. Fitting of the coarsening rate data to established models for Ostwald ripening additionally support this as a primary mechanism of coarsening.

Elemental sulfur sols coarsen rapidly at elevated temperatures and experience significant effects on both solubility and particle coarsening kinetics due to interaction with surfactants. Growth of elemental sulfur nanoparticles and sols is largely governed by Ostwald ripening processes.

We have studied the impact of dissolved aluminum on interfacial properties of two aluminum bearing minerals, corundum and kaolinite. The effect of intentionally adding dissolved aluminum on electrokinetic potential of basal plane surfaces of sapphire was studied by streaming potential measurements as a function of pH and was complemented by a second harmonic generation (SHG) study at pH?6. The electrokinetic data show a similar trend as the SHG data, suggesting that the SHG electric field correlates to zeta-potential. A comparable study was carried out on kaolinite particles. In this case electrophoretic mobility was measured as a function of pH. In both systems the addition of dissolved aluminum caused significant changes in the charging behavior. The isoelectric point consistently shifted to higher pH values, the extent of the shift depending on the amount of aluminum present or added. The experimental results imply that published isoelectric points of clay minerals may have been affected by this phenomenon. The presence of dissolved aluminum in experimental studies may be caused by particular pre-treatment methods (such as washing in acids and subsequent adsorption of dissolved aluminum) or even simply by starting a series of measurements from extreme pH (causing dissolution), and subsequently varying the pH in the very same batch. This results in interactions of dissolved aluminum with the target surface.

A possible interpretation of the experimental results could be that at low aluminum concentrations adatoms of aluminum (we will refer to adsorbed mineral constituents as adatoms) can form at the sapphire basal plane, which can be rather easily removed. Simultaneously, once the surface has been exposed to sufficiently high aluminum concentration, a visible change of the surface is seen by AFM which is attributed to a surface precipitate that cannot be removed under the conditions employed in the current study.

In conclusion, whenever pre-treatment or the starting point of an experiment favor the dissolution of aluminum, dissolved Al may remain in the experimental system and interact with the target surfaces. The systems are then no longer pristine and points of zero charge or sorption data are those of aluminum-bearing systems.

Procedures for the analysis of phosphorus in geological material normally aims for the determination of the total amount of P expressed as orthophosphate $�\left(�{�\text{PO}�}_{�4�}^{�3�-�}�\right)�$ or the differentiation between inorganic and organic P. This is probably due to analytical difficulties but also to the prevalent opinion that the chemistry of phosphorus in geological environments is almost entirely restricted to the mineral apatite. Because of the low solubility of apatite it is, therefore, commonly argued that little P was around for prebiotic chemistry and that pre-biological processes would essentially have had to do without this indispensable element unless it was provided by alternative sources or mechanisms (such as reduction and activation by lightning or delivery to Earth by celestial bodies). It is a paradox that the potential existence of reactive phosphorus compounds, such as the mineral schreibersite - iron phosphide, in geological material on Earth is seldom considered although we are aware of the existence of such compounds in meteorite material. The content of Al₂O₃ in rocks appears to be important for the speciation of phosphorus and for how strongly it binds to silicates. In general, low alumina seems to promote the existence of isolated charge-balanced phosphorus complexes.