Reactivity of various types of iron(III) (hydr)oxides towards light-induced dissolution

Laboratory experiments were conducted on the light-induced dissolution of three well defined Fe(III) (hydr)oxide phases (γ-FeOOH, α-FeOOH, and α-Fe₂O₃) with oxalate as reductant/ligand. Upon irradiation of an aerated γ-FeOOH suspension of pH 3, photooxidation of oxalate and photochemical formation of dissolved Fe(II) occurred according to a 1:1 stoichiometry. This was not observed with aerated α-FeOOH and α-Fe₂O₃ suspensions of pH 3, where photooxidation of oxalate was not accompanied by formation of appreciable concentrations of dissolved Fe(II). We hypothesize that in aerated α-FeOOH and α-Fe₂O₃ suspensions, oxidation of surface Fe(II) outcompetes its detachment from the crystal lattice. Also in deaerated suspensions, α-FeOOH and α-Fe₂O₃ behaved differently from γ-FeOOH with regard to light-induced dissolution. We interpret our results by assuming that light-induced dissolution of α-FeOOH and α-Fe₂O₃ in deaerated suspensions of pH 3 occurred mainly through Fe(II)-catalyzed thermal dissolution of the solid phases, where Fe(II) was initially formed by photoreductive dissolution and then predominantly via photolysis of dissolved Fe(III) oxalate complexes. With γ-FeOOH, on the other hand, dissolved Fe(II) formation occurred probably mainly through photochemical reductive dissolution under photooxidation of adsorbed oxalate. From our results we conclude that the efficiency of detachment of reduced surface iron is a key parameter of the overall kinetics of photoreductive dissolution of Fe(III) (hydr)oxides in aquatic systems, and that thermodynamically stable phases such as α-FeOOH and α-Fe₂O₃ are not readily dissolved in the presence of O₂, even at low pH-values and in the presence of light and reductants like oxalate. We propose that redox cycling of iron at the surface of crystalline Fe(III) (hydr)oxide phases, i.e. reduction and oxidation of surface iron without transfer into solution, may be an important pathway of transformation of thermodynamically stable atmospheric Fe(III) (hydr)oxides into less stable and thus more soluble phases.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

泰国湾西部表层沉积物自生矿物分布及组成

Generation, morphology, and distribution of authigenic minerals directly reflect sedimentary environment and material sources. Surface sediments were collected from the western Gulf of Thailand during 2011–2012, and 159 samples were analyzed to determine detrital minerals. Authigenic minerals, including siderite, pyrite, and glauconite, are abundant whereas secondary minerals, such as chlorite and limonite, are distributed widely in the study area. Siderite has a maximum content of 19.98 g/kg and appears in three types from nearshore to continental shelf, showing the process of forming-maturity-oxidation. In this process, the Mn O content in siderite decreases, but Fe_2O_3 and Mg O content increase. Colorless or transparent siderite pellets are fresh grains generated within a short time and widely distributed throughout the region; high content appears in coastal area where river inputs are discharged. Translucent cemented double pellets appearing light yellow to red are mature grains; high content is observed in the central shelf. Red-brown opaque granular pellets are oxidized grains,which are concentrated in the eastern gulf. Pyrite is mostly distributed in the central continental shelf with an approximately north–south strip. Pyrite are mainly observed in foraminifera shell and distributed in clayey silt sediments, which is similar to that in the Yangtze River mouth and the Yellow Sea. The pyrite in the gulf is deduced from genetic types associated with sulfate reduction and organic matter decomposition. Majority of glauconite are granular with few laminar. Glauconite is concentrated in the northern and southern parts within the boundary of 9.5° to 10.5°N and is affected by river input diffusion. The distribution of glauconite is closely correlated with that of chlorite and plagioclase, indicating that glauconite is possibly derived from altered products of chlorite and plagioclase. The K_2O content of glauconite is low or absent, indicating its short formation time.     

Iron geochemistry under mussel rafts in the Galician ria system (Galicia-NW Spain)

The intensive mussel culture carried out in the past 40 years in the Rias of Vigo and Arousa (Galicia-NW Spain) has led to substantial changes in the ecology and geochemistry of the seabed in these areas. Organic C enrichment of the seabed has generated strongly reducing conditions that directly affect the geochemistry of Fe and S. In the present study a total of six sediment cores were collected from the seabed under mussel rafts, and two different layers were distinguished: the biodeposit generated by the mussels, and the sediment situated immediately below this. Samples of each were analyzed to determine the pH, redox potential, sulphate and chloride in the interstitial water, as well as total percentage of organic C (TOC), N and S. Sequential extraction of the samples differentiated six fractions of Fe: exchangeable, carbonate, ferrihydrite, lepidocrocite, goethite and pyrite. The contents of total Fe, Fe associated with silicates, Fe soluble in 1 M HCl and AVS-Fe were also determined. In general, both the biodeposit and the sediment were anoxic (Eh < 100 mV) and there were no significant differences between the two in the total Fe or in the Fe associated with silicates, which appears to indicate that the input of Fe to the system did not vary greatly. However, there were significant differences between the sediment and the biodeposit in terms of the forms of Fe in each layer. The concentrations of pyrite in the biodeposit (0.37 ± 0.25 μmol g⁻¹) were high but significantly lower than in the sediment (1.10 ± 0.20 μmol g⁻¹), and there remained large quantities of reactive-Fe that were susceptible to pyritisation. In contrast, in the sediment, the reactive-Fe was intensively pyritised, and judging from the ratio of TOC–DOP, it limited synthesis of pyrite. Furthermore, a plot of the concentration of pyrite-S against TOC revealed an excess of ∼15% of pyrite-S, which is explained by the partial decoupling of pyrite formation from organic matter accumulation, caused by the formation of pyrite from the H₂S generated by the anaerobic oxidation of methane. The latter process also appears to favour, although to a lesser extent, the precipitation of Ca carbonate, with incorporation of Fe.     

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high SO²⁻₄ reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. δ³⁴S values of pyrite are −33‰ to −50‰. Below the sapropels δ³⁴S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.     

Authigenic iron oxide formation in the estuarine mixing zone of the Yangtze River

Estuaries are elementary geochemical fronts where river water and seawater mix. Within this mixing zone, iron and other non-conservative elements can undergo complex reactions to form new solid phases. In order to understand authigenic iron oxide formation in the Yangtze River Estuary, two onsite water-mixing sets of experiments were conducted, one by mixing variable amounts of unfiltered Yangtze River water with filtered East China Sea water of different salinity (set 1), the other by mixing variable amounts of filtered Yangtze River water with filtered East China Sea water of different salinity (set 2). In set 2, the minerals newly formed in the course of mixing were investigated by means of a scanning electron microscope fitted with an energy-dispersive X-ray analytical system. It was found that ferrihydrite and lepidocrocite were formed in these mixing experiments, coexisting in nearly equal amounts. These iron oxides appear as aggregated particles with a large grain-size range of several microns to more than 100 μm. The electrolytic properties of seawater played an important role in the formation of these authigenic iron oxides. Kaolinite and organic aggregates were also found in the experimentally mixed pre-filtered waters. Amounts of newly formed suspended matter (set 2) were one to three orders of magnitude lower than those of total suspended matter (TSM) (set 1). This implies that newly formed minerals represent only a very small proportion of TSM in the estuarine mixing zone of the Yangtze River.     

Relationship between sinking organic matter and minerals in the shallow zone of the western Subarctic Pacific

We used time-series sediment trap data for four major components, organic matter and ballast minerals (CaCO₃, opal, and lithogenic matter) from 150, 540, and 1000 m in the western subarctic Pacific (WSAP), where opal is the predominant mineral in sinking particles, to develop four simple models for settling particles, including the “ballast model”. The ballast model is based on the concept that most of the organic matter “rain” in the deep sea is carried by the minerals. These four models are designed to simultaneously reproduce the flux of each major component of settling particles at 540 and 1000 m by using the data for each component at 150 m as initial values. Among the four models, the ballast model, which considers the sinking velocity increase with depth, was identified as the best using the Akaike information criterion as a measure of the model fit to data. This model successfully reproduced the flux of organic matter at 540 and 1000 m, indicating that the ballast model concept works well in the shallow zone of the WSAP on a seasonal timescale. This also suggests that ballast minerals not only physically protect the organic matter from degradation during the settling process but also enhance the sinking velocity and reduce the degree of decomposition.     

Enhanced preservation of organic matter in sediments deposited within the oxygen minimum zone in the northeastern Arabian Sea

The presence of a strongly developed oxygen minimum zone (OMZ; [O₂]<2 μM) in the northeastern Arabian Sea affords the opportunity to investigate whether oxygen deficiency in bottom waters enhances the preservation of organic matter in the underlying sediments. We explored if the observed patterns of organic matter accumulation could be explained by differences in productivity, sedimentation rate, water depth, and mineral texture. The differences in the burial rates of organic matter in sediments deposited within or below the OMZ could not be explained on the basis of these factors. All collected evidence points to a coupling of low oxygen concentrations and enhanced organic matter preservation. Under more oxygenated conditions bioturbation as well as the presence of labile manganese and iron oxides are probably important factors for a more efficient microbially mediated degradation of organic matter. Pore water profiles of dissolved Mn²⁺ and Fe²⁺ show that reduction of manganese and iron oxides plays a minor role in sediments lying within the OMZ and a larger role in sediments lying below the OMZ.     

Analysis and distribution of iron sulfide minerals in recent anoxic marine sediments

Acid-volatile sulfide (AVS), pyrite-sulfur, iron and organic carbon distributions were examined in sediments from a variety of oxic and anoxic marine environments. Multiple determinations of AVS using different acid conditions showed that most extractants give similar AVS concentrations, with the exception of stannous chloride in hot HCl which digested between 10 and 81% of pyrite-sulfur.An extensive examination of iron sulfide minerals in sediments, using scanning electron microscopy combined with simultaneous elemental analysis, showed that identifiable iron sulfides were almost always pyrite. Occurrence of greigite observable by SEM was limited to one site and mackinawite was not found in any samples. Thus, if these minerals are precursors to pyrite formation, as has been frequently hypothesized, they must be primarily present as coatings on other mineral grains or submicron particles.     

BIB-SEM characterization of pore space morphology and distribution in postmature to overmature samples from the Haynesville and Bossier Shales

Four Haynesville Shale and four Bossier Shale samples were investigated using a combination of Scanning Electron Microscopy (SEM) and Broad Ion Beam (BIB) polishing. This approach enables the microstructure and porosity to be studied down to the mesopore size (<50 nm) in representative areas at the scale of the BIB cross-sections. The samples vary in mineralogy, grain size and TOC and the maturity ranges from 2.42 to 2.58 VR_r in the Haynesville Shale to 1.79–2.26 VR_r in the Bossier Shale. This variety within the samples enabled us to study controls on the porosity distribution in these shales. Visible pores exist as intraparticle pores mainly in carbonate grains and pyrite framboids and as interparticle pores, mainly in the clay-rich matrix. Pores in organic matter show a characteristic porosity with respect to the type of organic matter, which mainly consists of mixtures of amorphous organic matter and minerals, organic laminae and discrete macerals. A clear positive trend of organic-matter porosity with maturity was found. Pore sizes are power law distributed in the range of 4.4 μm to at least 36 nm in equivalent diameter. The differences in power law exponents suggest that a more grain supported, coarse-grained matrix may prevent pores from mechanical compaction. Porosities measured in the BIB cross-sections were significantly lower in comparison to porosities obtained by Mercury Intrusion Porosimetry (MIP). This difference is mainly attributed to the different resolution achieved with BIB-SEM and MIP and type of pore network. Extrapolation of pore size distributions (PSDs) enables the BIB-SEM porosity to be estimated down to the resolution of the MIP and thus to upscale microstructural observation at the confined space of the BIB-SEM method to bulk porosity measurement. These inferred porosities are in good agreement with the MIP determined porosities, which underpins the assumption that pores segmented in BIB-SEM mosaics are representative of the MIP methodology.     

Sulphide mineralisation in the deep sea hydrothermal vent polychaete, Alvinella pompejana: implications for fossil preservation

Hydrothermal vent fauna, particularly vestimentiferan and polychaete worm tubes, are occasionally preserved in the geological record. The early stages of mineralisation are particularly important in defining whether or not preservation will occur, and they are poorly understood. Tube samples of the polychaete worm Alvinella pompejana collected from 13°N on the East Pacific Rise have been studied to identify the processes occurring during early pyrite/marcasite mineralisation. Iron sulphide mineralisation is present within the walls of the organic dwelling tube, and is induced by microbial fauna preserved within the tube micro-layers. Various microorganisms were observed coating the inner tube surfaces, together with 10-100 μm-sized Fe- and Zn-sulphide particles precipitated from vent fluids. The microbes and particulate sulphides become entombed within the tube wall as further layers of organic material are secreted by the worm, during tube-building episodes. This results in a laminated tube structure being formed, composed of alternating layers of tube material and microbial/sulphide-rich interlayers. The microbial/sulphide layers provide a template for further mineralisation and replacement of the microbes with pyrite while degradation of the organic components occurs. The iron monosulphides mackinawite and greigite have been identified as intermediatory phases that occur as precursor minerals during the formation of pyrite. Later marcasite mineralisation is observed to form over some of the pyritised organic layers. Once mineralisation has replaced most of the organic tube material, the structure will then be preserved along with the host sulphide body. These observations enhance our understanding of the mechanisms of fossil pyritisation in fine-scaled organic structures throughout the geological record.     

The Significance of Diagenesis versus Riverine Input in Contributing to the Sediment Geochemical Matrix of Iron and Manganese in an Intertidal Region

Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (r_s), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (r_s=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (r_s=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.     

2D and 3D nanopore characterization of gas shale in Longmaxi formation based on FIB-SEM

Studying complex pore structures is the key to understanding the mechanism of shale gas accumulation. FIB-SEM (focused ion beam-scanning electron microscope) is the mainstream and effective instrument for imaging nanopores in gas shales. Based on this technology, 2D and 3D characteristics of shale samples from Lower Silurian Longmaxi formation in southern Sichuan Basin were investigated. 2D experimental results show that the pores in shale are nanometer-sized, and the structure of those nanopores can be classified into three types: organic pores, inorganic pores and micro fractures. Among the three types, organic pores are dominantly developed in the OM (organic matter) with three patterns such as continuous distributed OM, OM between clay minerals and OM between pyrite particles, and the size of organic pores range from 5 nm to 200 nm.Inveresly, inorganic pores and micro fractures are less developed in the Longmaxi shales. 3D digital rocks were reconstructed and segmented by 600 continuous images by FIB cutting and SEM imaging simultaneously. The pore size distribution and porosity can be calculated by this 3D digital core, showing that its average value is 32 nm and porosity is 3.62%.The 3D digital porosity is higher than its helium porosity, which can be regarded as one important parameter for evaluation of shale gas reserves. The 2D and 3D characterized results suggest that the nanometer-sized pores in organic matter take up the fundamental storage space for the Longmaxi shale. These characteristics have contributed to the preservation of shale gas in this complex tectonic area.     

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.     

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

腐殖酸在海水/矿物界面上的吸附行为

用批量平衡实验法研究了腐殖酸(Humic acid,HA)在4种矿物蒙脱石、高岭石、针铁矿和水锰矿上的吸附。Freundlich和Langmuir模型都可以很好地描述吸附行为。矿物对腐殖酸的吸附能力顺序为:针铁矿水锰矿蒙脱石高岭石。增大盐度有利于促进吸附,但溶解有机质对吸附影响很小。腐殖酸在蒙脱石、高岭石和水锰矿3种矿物上的吸附随溶液pH值的升高而减少,而在针铁矿上的吸附只有当pH值高于7时才逐渐降低。腐殖酸在矿物表面上的作用机制最可能是疏水作用和氢键作用。     

Sedimentary sulfides in the Nearshore Georgia Bight

Sedimentary sulfide, iron, and organic matter were measured in neritic sediments from the Georgia Bight. The two measured depth integrated sulfur pools, FeS + HS⁻ and FeS₂, tended to decrease with increasing distance from shore out to 33 km. Total iron and organic matter were strongly correlated and both tended to decrease with increasing distance from shore. Sediment depth profiles of organic matter/reduced sulfur suggest relatively constant rates of sulfate reduction over the top 40 cm of sediment. Differences in within-station variance indicated regions of lower and higher spatial/temporal heterogeneity, that may be related to tidally driven circulation patterns. No seasonal cycles were evident in sedimentary sulfides.     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Smectite formation in metalliferous sediments near the East Pacific Rise at 13°N

A 43 cm long E271 sediment core collected near the East Pacific Rise(EPR) at 13°N were studied to investigate the origin of smectite for understanding better the geochemical behavior of hydrothermal material after deposition.E271 sediments are typical metalliferous sediments. After removal of organic matter, carbonate, biogenic opal,and Fe-Mn oxide by a series of chemical procedures, clay minerals(2 μm) were investigated by X-ray diffraction,chemical analysis and Si isotope analysis. Due to the influence of seafloor hydrothermal activity and close to continent, the sources of clay minerals are complex. Illite, chlorite and kaolinite are suggested to be transported from either North or Central America by rivers or winds, but smectite is authigenic. It is enriched in iron, and its contents are highest in clay minerals. Data show that smectite is most likely formed by the reaction of hydrothermal Fe-oxyhydroxide with silica and seawater in metalliferous sediments. The Si that participates in this reaction may be derived from siliceous microfossils(diatoms or radiolarians), hydrothermal fluids, or detrital mineral phases. And their δ30 Si values are higher than those of authigenic smectites, which implies that a Si isotope fractionation occurs during the formation because of the selective absorption of light Si isotopes onto Feoxyhydroxides. Sm/Fe mass ratios(a proxy for overall REE/Fe ratio) in E271 clay minerals are lower than those in metalliferous sediments, as well as distal hydrothermal plume particles and terrigenous clay minerals. This result suggests that some REE are lost during the smectite formation, perhaps because their large ionic radii of REE scavenged by Fe-oxyhydroxides preclude substitution in either tetrahedral or octahedral lattice sites of this mineral structure, which decreases the value of metalliferous sediments as a potential resource for REE.