Surrounding Pore Water Research Articles

Formation of dolomites from the newly discovered ancient cold seep in the Middle Dongsha area of the South China Sea

Remotely operated vehicle (ROV) observations have recently revealed seep dolomite deposits covering the seafloor on Middle Dongsha of the South China Sea (SCS). Spurred by these findings, we studied the mineralogical and geochemical properties to examine the seep dolomite’s origin, precipitation mechanism, and formation environment. These carbonates mainly comprise dolomite (from 64 to 84 wt%), followed by small amounts of calcite (from 1 to 3 wt%), locally containing magnesite (∼4 wt%), and goethite (∼14 wt%). Extensively developed mineralized cells containing high Mg and Ca contents found in chimneys imply that microbially-mediated processes probably participated in the reactivation of dolomite precipitation. The moderate and concentrated δ13C values (from −36.64 to −39.16‰, V-PDB) indicated that the carbon in carbonates was mainly derived from thermogenic methane. The methane fluids most likely ascended beneath the volcaniclastic unit and inherited enriched positive Eu anomalies due to fluid–rock interactions during their seepage along tectonic faults to the seafloor. The δ18O values (4.2–4.8‰, V-PDB) of carbonate suggested that an 18O-depleted fluid was involved in carbonate precipitation. The high total Rare-Earth Element contents (ΣREE) of seep carbonates varied from 61 ppm to 92 ppm, reflecting the chemical composition of surrounding pore waters at the time of carbonate precipitation, exhibiting less mixing with seawater. It may also indicate higher alkalinity and pH of the pore water. Although the sea-like REE patterns (HREE-enriched, negative Ce anomalies) are not caused by seawater, they may be due to the complexation competition between humic acid (HA) and carbonate for REE at high pore-water alkalinity and high CO32− concentrations. This is consistent with the dolomite chimney pointing toward a formation environment in relatively deep sediments, in particular, close to the sulfate-methane interface in sediments, where the bicarbonate concentration reaches its maximum due to AOM. Moderate Mo and no U enrichments appeared in the carbonates, suggesting a relatively lower intensity of methane seepages with relatively reduced AOM rates. The wide range of (Mo/U)EF values and U–Mo covariation indicates the very dynamic AOM rate (slow to moderate) and redox conditions (mostly suboxic–anoxic, occasionally sulfidic conditions) during carbonate formation due to episodically changing seepage activity.

In situ arsenic immobilization by natural iron (oxyhydr)oxide precipitates in As–contaminated groundwater irrigation canals

Arsenic-contaminated groundwater is widely used in agriculture. To meet the increasing demand for safe water in agriculture, an efficient and cost-effective method for As removal from groundwater is urgently needed. We hypothesized that Fe (oxyhydr)oxide (FeOOH) minerals precipitated in situ from indigenous Fe in groundwater may immobilize As, providing a solution for safely using As-contaminated groundwater in irrigation. To confirm this hypothesis and identify the controlling mechanisms, we comprehensively evaluated the transport, speciation changes, and immobilization of As and Fe in agricultural canals irrigated using As-contaminated groundwater. The efficiently removed As and Fe in the canals accumulated in shallow sediment rather than subsurface sediment. Linear combination fitting (LCF) analysis of X–ray absorption near edge spectroscopy (XANES) indicated that As(V) was the dominant As species, followed by As(III), and there was no FeAsO4 precipitate. Sequential extraction revealed higher contents of amorphous FeOOH and associated As in shallower sediment than in the subsurface layer. Stoichiometric molar ratio calculations, SEM‒EDS, FTIR, and fluorescence spectroscopy collectively demonstrated that the microbial reductive dissolution of amorphous FeOOH proceeded via reactive dissolved organic matter (DOM) consumption in subsurface anoxic porewater environment facilitating high labile As, whereas in surface sediment, the in situ-generated amorphous FeOOH was stable and strongly inhibited As release via adsorption. In summary, groundwater Fe2+ can efficiently precipitate in benthic surface sediment as abundant amorphous FeOOH, which immobilizes most of the dissolved As, protecting agricultural soil from contamination. This field research supports the critical roles of the phase and reactivity of in situ-generated FeOOH in As immobilization and provides new insight into the sustainable use of contaminated water.

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

The compressive behaviours and microscopic characteristics of deep-sea soft soil with deionized or sea water

To investigate the effects of different pore water environments on compressive behaviours of the deep-sea soft soil from South China Sea, four kinds of soil samples including natural sample with sea water or deionized water, remolded sample with sea water or deionized water were prepared, respectively. Then, a series of oedometer tests and scanning electron microscopy tests were performed on the above samples to examine their compressive behaviours and microscopic characteristics, respectively. Additionally, the microscopic pore distribution of natural sample with sea water was observed by mercury intrusion porosimetry tests. The effects of different water environments on macroscopic compressive behaviours and microscopic particle characteristics are analyzed. The deionized water environment increases the compressibility and decreases the consolidation coefficient for natural samples after structural breakage and remolding. The microscopic particle characteristics corresponding to the macroscopic compressibility are also qualitatively analyzed. In deionized water environment, soil particles exhibit higher roundness, more orderly and lower surface roughness than that in seawater environment. In this study, the deionized water environment has no obvious effect on the structural yield stress and secondary consolidation coefficients of deep-sea soft soil.

The formation environment of Carboniferous karstic bauxite deposits in the central North China Craton: Insights from nitrogen isotopes and geochemical proxies

Over 5 billion tons of karstic bauxites are hosted in the Late Carboniferous Benxi Formation in the North China Craton (NCC). However, the bauxite formation environment in the central NCC remains unknown. The geological, mineralogical, geochemical, nitrogen concentrations, and δ15N isotope evidence of the Huilong and Shangwutou bauxite deposits in the central NCC was conducted, aiming to clarify the formation environments. Typically, bauxites in the central NCC contains three layers from bottom to top: Fe-bearing claystone/clayey ironstone, bauxite ore, and bauxitic claystone. The Fe-bearing claystone/clayey ironstone is composed of kaolinite, goethite, and hematite; the bauxite ore is composed of diaspore, kaolinite, but also minor hematite, ilmenite, and svanbergite; and the bauxitic claystone consists of kaolinite, but also some diaspore and goethite. Diaspores coexisted extensively with hematite, anatase, and svanbergite, forming cryptocrystalline matrix of bauxites, suggesting that they may be formed during early diagenesis. Geochemical discriminant diagrams also indicated that two deposits were primarily affected by the hydrogenous deposition and early diagenesis, and no sedimentary recirculation. The ∑REEs concentrations and fractionation (Prn/Ybn) features along the profiles mainly concentrated in the bottom bauxite ore, which reflected that the pH values could be alkaline in bottom bauxite ore, and decreased weakly acidic for the central bauxite ore to bauxitic claystone along the profiles upwards. Combining the δ15N data with two geochemical redox proxies, and the widely coexistence of diaspore and hematite, indicated that the two deposits mainly formed under suboxic conditions, and thus denitrification was the predominant process in nitrogen cycling. The δ15N values are positively correlated with paleosalinity proxies, indicating that the higher saline bottom water may lead to a strong vertical density differential and water-column stratification, conducing to forming suboxic restricted pore-water environments.

Impact of variable density on electrokinetic transport and mixing in porous media

Electrokinetic (EK) techniques can effectively mobilize amendments and contaminants in porous media and therefore have a great potential for in situ subsurface remediation of a wide variety of organic and inorganic contaminants. However, the fundamental mechanisms governing EK applications in porous media are complex and entail coupling between different flow, transport, electrostatic and geochemical processes. In this study we investigate the interactions between density driven effects and electrokinetic transport in permeable porous media and we compare the observed dynamics with the outcomes of analogous scenarios in which advection and dispersion are the only transport mechanisms. We perform a series of multidimensional experiments and we demonstrate the strong interplay between Coulombic interactions among charged species in pore water and density-driven effects during electrokinetics. Our study illuminates non-trivial interactions between the pore water composition and the macroscopic behavior of variable density dye tracer plumes, showing different sinking and floating patterns, distinct plume shapes and spreading, as well as different extent of mixing depending on the chemical composition of the pore water. A numerical model, based on the Nernst-Planck-Poisson formulation and on the coupling with the geochemical code PHREEQC, was developed to simulate variable density flow and transport and to update the density of the aqueous solution resulting from mixing and electrostatic interactions between all chemical species in the injected plume and in the surrounding pore water electrolyte. The model allowed us to interpret the experiments and to visualize the impact of small density gradients and Coulombic effects on the macroscopic transport of the dye tracer. The outcomes of this study highlight the importance of density-driven flow also during EK transport, where the electrostatic interactions not only influence the concentration of charged species but can also affect the density and result in complex flow patterns, plume shapes and mixing behavior, radically different from the ones generated during advective-dispersive transport.

Sedimentology and geochemistry of basinal lithofacies in the Mesoarchean (2.93 Ga) Red Lake carbonate platform, northwest Ontario, Canada

The > 200 m thick Red Lake carbonate platform of the 2.940-2.925 Ga Ball Assemblage (Red Lake Greenstone Belt, Superior Province, Canada) is the oldest known carbonate platform preserved on Earth. This study examined surface outcrops and multiple industry cored drill holes comprising a diverse assemblage of chemical and siliciclastic sedimentary rocks of the deeper water lithofacies associated with the shallow water carbonates. The offshore lithologies, underlying, interlayered with, and overlying the mainly stromatolitic carbonates, consist of alternating packages of sandstone, siltstone, carbonaceous slate, pyritic carbonaceous slate, chert, and oxide facies iron formation (OFIF). These interlayer with carbonate in transitional slope environments, which consist in places of carbonate with magnetite laminae above slumped carbonate debris in iron formation and/or carbonaceous slate. Chert and OFIF were deposited further offshore in a suboxic environment, with lithology dependent on concentrations of seawater Fe(II) and silicic acid. The iron sulfides were deposited in a reducing, anoxic, and organic-rich bottom water and muddy pore water environment not conducive to Fe hydroxide or chert precipitation. Carbonaceous mud was the background sediment, accumulating during intervals when the precipitation of chert, Fe hydroxides, or massive layers of Fe sulfides was inhibited. The interlayering of differing assemblages of chemical and siliciclastic sedimentary rocks indicates temporal and spatial fluctuations in the chemistry of local paleo-seawater and variable sedimentation rates on the margins of the Red Lake carbonate platform. Post-Archean Australian Shale (PAAS)- normalized rare earth element (REE) systematics of carbonate and OFIF show positive La and Gd anomalies, super-chondritic Y/Ho ratios, and depleted light rare earth elements (LREEs) relative to heavy rare earth elements (HREEs), similar to modern seawater, while the positive Eu anomalies in the carbonate and OFIF samples reflect hydrothermally influenced Archean seawater. The chemical sedimentary rocks exhibit enrichment of redox-sensitive elements (i.e., Cr, Mo, V, and U) compared to their siliciclastic associates. This, combined with concentrations of MnO up to 6.3 wt% and positive Ce anomalies in the iron formation directly below the carbonate platform, all indicate the likely presence of some O2 ca 2.93 Ga.

A method for a fast and economical in situ collection of pore water in sandy sediments

Marine sediment represents one of the most significant carbon reservoirs. Extraction of pore water from the uppermost 10 cm of the sediment column, just below the sediment-water interface, in coastal environments can be used to assess the rapid chemical changes caused by extensive subsurface biological and chemical reactions. However, owing to relatively large grain size of the sediment in some shallow coastal environments, sediment and pore water mixes quickly making collection of core samples for pore water extraction extremely difficult. Here, we present a simple method utilizing Rhizons to collect in situ pore water from coastal environments. We conducted both ex situ and in situ experiments, using fluorescein as a tracer, to understand the influence of overlying water during pore water collection through this method. These experiments also allowed us to assess the volume of pore water collected before fluorescein is observed in the samples at different vertical depths within the sediment column. We found that: 1. discarding the initial 2 mL of water minimizes the memory effect, 2. collection of 10 mL of water avoids interference from surrounding pore water and the overlying water column and 3. a vertical resolution of minimum 2 cm could be attained for sediments with grain size of 1 mm and less. We finally present data from two linear transects from different sites in the Gulf of Aqaba. Results from these case studies demonstrate expected patterns of high concentrations of iron and hydrogen sulfide in pore water from the sediment where surface coloration suggested iron and sulfate reduction was dominating, respectively. Both case studies, therefore, independently validated the Rhizon sampler method for collecting pore water in situ from marine sediments in coastal environments.

Upper Ediacaran fibrous dolomite versus Ordovician fibrous calcite cement: Origin and significance as a paleoenvironmental archive

Fibrous carbonate cement is a common phase in marine phreatic environments — but its origin and diagenetic history are underexplored. This paper compares two fibrous fabrics that are different in terms of their peculiarities but share important similarities regarding their essentials: upper Ediacaran fibrous dolomite cement and Upper Ordovician fibrous calcite cement, both from the Tarim Basin, China. The focus is on the significance of these fabrics as archives of their marine paleoenvironment. Upper Ediacaran fibrous dolomite cement is present as (i) a fascicular-optic and (ii) a radial-fibrous phase. Judging from the optical length-slow character and luminescent zones, radial-fibrous dolomite cement precipitated directly from early diagenetic marine porewater. Fascicular-optic dolomite cement has a length fast optical character and hence likely formed as a high-Mg calcite precursor penecontemporaneously in a reefal, shallow-marine diagenetic environment. Similarly, two types of Upper Ordovician fibrous cement are present: (i) radiaxial-fibrous and (ii) fascicular-optic calcite cement. Fascicular-optic calcite precipitated in a marine phreatic platform environment, whereas radiaxial-fibrous calcite cement formed in an early marine diagenetic porewater environment. Both fabrics arguably replace a magnesium calcite precursor. For the case of the Tarim Basin, cathodoluminescence and redox-sensitive elements indicate predominantly anoxic, upper Ediacaran marine waters (Ce anomaly = 0.8 ± 0.2), and suboxic, Upper Ordovician shallow-marine seawater (0.7 ± 0.2). Based on PHREEQC modeling, the shallow burial, upper Ediacaran porewater (5.1) yields a higher dolomite saturation index than upper Ediacaran (4.8) and Upper Ordovician seawater (3.7). The direct precipitation of radial-fibrous dolomite from Ediacaran porewaters was likely induced due to organic matter decomposition and related seawater oxygen depletion, elevated Mg2+/Ca2+ ratios, and high alkalinity values. Modeling and proxy data show significant hydrogeochemical differences between seawater and porewater in the upper meters of the sediment column. The upper Ediacaran seawater apparently favored fibrous cement formation with magnesium calcite precursors. In contrast, fibrous dolomite cement was directly precipitated in an early-diagenetic marine porewater regime. The comparability of proxy data reflecting seawater and such recording early diagenetic marine porewater is critically discussed.

Morphological characterisation of ash particles from co-combustion of sewage sludge and wheat straw with X-ray microtomography.

Combustion of phosphorus-rich residual streams can produce nutrient-rich ashes and these can be used either in further processing or as materials for direct nutrient recycling. The latter requires knowledge on morphological parameters of such ash particles that may impact plant growth, nutrient availability, and soil physical properties. The present work aims to determine the porosity, pore size, and specific surface area of ash particles, and discuss these properties in light of literature concerning interaction with soil water and plant roots. Bottom ash particles from combustion of sewage sludge and wheat straw and their co-combustion were analysed with X-ray microtomography. Image analysis provided information on morphology, specific surface area, porosity, and pore structure on a micrometre scale resolution. Co-combusting sewage sludge with wheat straw resulted in differences in ash particles' porosity and pore structure compared to combustion of pure fuels. Pure wheat straw ash displayed 62vol% porosity while there was no apparent difference between 10wt% or 30wt% mixtures of sewage sludge, with a porosity of 29-31vol%. Open pore volume comprise the largest part of the porosity (72-99vol%) enabling interaction between surrounding pore water and nutrients. Overall, the ash particles display large open volume fractions and thin particle walls which may lead to rapid weathering and extensive interaction with soil water. The particles generally contained pore openings over 200µm towards the surroundings, which provide opportunities for interaction with microbes and roots from a variety of plant species in addition to nutrient transport by soil water.

Iron speciation in organic-rich shales from the Upper Triassic Yanchang Formation, Ordos Basin, Northern China: Implications for depositional environment

The iron (Fe) cycle is one of the most important marine and lacustrine geochemical cycles and is closely related to environmental redox conditions, which directly affects carbon, sulfur, phosphorus cycling. Analysis of Fe speciation (including Feox, Femag, Fecarb, and Fepy) of organic-rich shale samples provides new insights into the controversial redox conditions during the Chang 7 sedimentary period. Our results show that Fecarb and Fepy of the Chang 7 organic-rich shale are the main forms of reactive Fe pools, indicating that reactive Fe mainly existed in the form of Fe2+ in sediments. With a few exceptions, most samples fall into the ferruginous region in crossplots of Fepy/FeHR versus FeHR/FeT, indicating that pore water environments during early diagenesis were ferruginous accompanied by intermittent euxinic. Previous works examining the size of framboidal pyrite, the molar ratio of organic carbon and total phosphorus (P), and nitrogen isotope values suggest the bottom water environments conditions were oxic-suboxic accompanied by intermittent anoxic. We argue these patterns may be explained by the proximity of the redox boundary of depositional environment to the sediment–water interface during most of the Chang 7 period, with short-term fluctuations. Euxinic pore water conditions correspond to anoxic bottom water conditions and elevated total organic carbon (TOC) content, indicating that these environmental conditions would increase the flux of P diffused from sediments. As a result, lacustrine primary productivity would be elevated, creating conditions conducive to the accumulation of organic matter that is characteristic of the Chang 7 sedimentary period. This work will further our understanding of the accumulation mechanism of organic matter in the Chang 7 shale, the principal source rock for the Mesozoic oil-bearing system in the Ordos Basin.

Neutron scattering quantification of unfrozen pore water in frozen mud

The Earth's polar regions are experiencing a greater frequency of freeze-thaw events throughout the polar summer, contributing to atmospheric methane and destabilising clay-rich sediments. Clays in soils tightly bind pore water and thus substantially modify freeze-thaw events. While temperatures of phase transitions for confined pore water may be precisely assessed using calorimetric or thermal analyses to −30 or −40 °C, neutron scattering directly probes how pores in clay minerals control ice formation and melting to lower temperatures. We apply elastic neutron scattering to accurately quantify the unfrozen water content of clay gels and unambiguously identify different pore-water environments by their freezing temperatures. Using this approach, we conclude that cryosuction controls water mobility in frozen soils in the absence of soluble salts to much lower temperatures than observed by other techniques. Dyanmics determined from neutron scattering indicates that water in clay gel pores thaws at much lower temperatures than currently considered, and thus pose potential risks for contaminant migration at sub freezing temperatures. The general poor strength of wet clays can significantly impact infrastructure in cold regions undergoing an increased frequency of freeze-thaw events. Different pore water environments in clay gels can be identified and quantified by inelastic neutron scattering. • Cryosuction removes interlayer water from clay gels hydrated to near saturation. • Cryosuction requires capillary connectivity to operate in clay gels. • Considerable interlayer water remains unfrozen in clay gels to below −80C. • Freezing characteristic curves can be used to identify pore environments.

Ore Genesis of the Takatori Tungsten–Quartz Vein Deposit, Japan: Chemical and Isotopic Evidence

The Takatori hypothermal tin–tungsten vein deposit is composed of wolframite-bearing quartz veins with minor cassiterite, chalcopyrite, pyrite, and lithium-bearing muscovite and sericite. Several wolframite rims show replacement textures, which are assumed to form by iron replacement with manganese postdating the wolframite precipitation. Lithium isotope ratios (δ7Li) of Li-bearing muscovite from the Takatori veins range from −3.1‰ to −2.1‰, and such Li-bearing muscovites are proven to occur at the early stage of mineralization. Fine-grained sericite with lower Li content shows relatively higher δ7Li values, and might have precipitated after the main ore forming event. The maximum oxygen isotope equilibrium temperature of quartz–muscovite pairs is 460 °C, and it is inferred that the fluids might be in equilibrium with ilmenite series granitic rocks. Oxygen isotope ratios (δ18O) of the Takatori ore-forming fluid range from +10‰ to +8‰. The δ18O values of the fluid decreased with decreasing temperature probably because the fluid was mixed with surrounding pore water and meteoric water. The formation pressure for the Takatori deposit is calculated to be 160 MPa on the basis of the difference between the pressure-independent oxygen isotope equilibrium temperature and pressure-dependent homogenization fluid inclusions temperature. The ore-formation depth is calculated to be around 6 km. These lines of evidence suggest that a granitic magma beneath the deposit played a crucial role in the Takatori deposit formation.

What process causes the slowdown of pressure solution creep

The slowdown of pressure solution creep has been thought to be caused by stress redistribution. This study presents a fresh view towards this creep behaviour. Basically, two rate-limiting mechanisms come into play amid pressure solution creep: (1) stress redistribution across expanding inter-granular contacts and (2) solute accumulation in the water film. Because non-hydrostatic dissolution occurs under open system conditions, solute accumulation in the water film is constrained by the ensuing solute transport process. Relying on the matter exchange across the contact surface boundary, the active processes in the voids, e.g., solute migration and deposition, affect pressure solution creep. Based upon the above, we sum up two requirements that have to be met for achieving chemical compaction equilibrium: (1) the Gibbs free energy of reaction, i.e., the driving force of non-hydrostatic dissolution process, gets depleted and (2) the concentration gradient between the water film and surrounding pore water vanishes.HighlightsThe slowdown of pressure solution creep is a combined result of stress migration across contacts and solute accumulation in the water film.Matter exchange with the surroundings inhibits solute accumulation in the water film.This article identifies two prerequisites that need to be fulfilled for achieving chemical compaction equilibrium.

Laboratory Experimental Study on the Formation of Authigenic Carbonates Induced by Microbes in Marine Sediments

Authigenic carbonates are widely distributed in marine sediments, microbes, and anaerobic oxidation of methane (AOM) play a key role in their formation. The authigenic carbonates in marine sediments have been affected by weathering and diagenesis for a long time, it is difficult to understand their formation process by analyzing the samples collected in situ. A pore water environment with 10 °C, 6 MPa in the marine sediments was built in a bioreactor to study the stages and characteristics of authigenic carbonates formation induced by microbes. In experiments, FeCO3 is formed preferentially, and then FeCO3-MgCO3 complete isomorphous series and a small part of CaCO3 isomorphous mixture are formed. According to this, it is proposed that the formation of authigenic carbonates performed by AOM and related microbes needs to undergo three stages: the rise of alkalinity, the preferential formation of a carbonate mineral, and the formation of carbonate isomorphous series. This work provides experimental experience and reference basis for further understanding the formation mechanism of authigenic carbonates in marine sediments.

A Numerical Investigation of the Deformation Mechanism of a Large Metro Station Foundation Pit under the Influence of Hydromechanical Processes

Considering the unique conditions of deep and large subway foundation pit excavation affected by heavy rainfall in soil-rock composite strata, this paper employs finite element numerical simulation methods to study foundation pit instability under the influence of heavy rainfall. According to the hydraulic coupling conditions caused by rainfall, a fluid-solid coupling numerical model for a deep and large subway foundation pit in soil-rock composite strata is established in this paper. By selecting the Anshan road station of Qingdao subway line 4 as the engineering background, various parameters related to foundation pit excavation affected by heavy rainfall at different excavation depths were analyzed. The study found that after the foundation pit was excavated, the surrounding pore water pressure decreased and the pore water pressure near the ground surface increased rapidly due to rainfall. As the horizontal distance from the foundation pit increased, the pore water pressure at the same depth also increased. The excavation of the foundation pit caused uplift of the bottom of the pit. After rainfall, the uplift value decreased compared with that before rainfall. With increasing excavation depth, the decreased value of the bottom uplift decreased and then increased. The rainfall caused the horizontal displacement of the pit walls on both sides of the pit to increase. When the excavation depth was 10 m, the horizontal displacements on both sides of the pit were equivalent. When the excavation depth was 20 m, the horizontal displacement was concentrated in the first 10 m; when the excavation depths were 30 m and 40 m, the horizontal displacement was concentrated in the first 13 m. This finding shows that when the foundation pit was affected by rainfall, the sidewall collapsed at a distance of 13 meters from the ground. As the excavation depth increased, the depth of excavation instability was closer to the bottom of the pit. The research in this paper can provide a reference for the construction of deep and large foundation pits in similar composite ground conditions that are affected by rainfall.

A cross scale investigation of galena oxidation and controls on mobilization of lead in mine waste rock

Galena and Pb-bearing secondary phases are the main sources of Pb in the terrestrial environment. Oxidative dissolution of galena releases aqueous Pb and SO4 to the surficial environment and commonly causes the formation of anglesite (in acidic environments) or cerussite (in alkaline environments). However, conditions prevalent in weathering environments are diverse and different reaction mechanisms reflect this variability at various scales. Here we applied complementary techniques across a range of scales, from nanometers to 10 s of meters, to study the oxidation of galena and accumulation of secondary phases that influence the release and mobilization of Pb within a sulfide-bearing waste-rock pile. Within the neutral-pH pore-water environment, the oxidation of galena releases Pb ions resulting in the formation of secondary Pb-bearing carbonate precipitates. Cerussite is the dominant phase and shannonite is a possible minor phase. Dissolved Cu from the pore water reacts at the surface of galena, forming covellite at the interface. Nanometer scale characterization suggests that secondary covellite is intergrown with secondary Pb-bearing carbonates at the interface. A small amount of the S derived from galena is sequestered with the secondary covellite, but the majority of the S is oxidized to sulfate and released to the pore water.

An Early Triassic small shelly fossil-style assemblage from the Virgin Limestone Member, Moenkopi Formation, western United States

Small shelly fossils (SSFs) are minute fossils moulded or replaced by apatite, and less commonly, other minerals like glauconite and iron oxides. This taphonomic mode is best known from Cambrian deposits, though some occurrences occur across geological time. Instances of small shelly-style preservation were found in insoluble residues from the Lower Triassic Virgin Limestone Member exposed in southern Nevada, the western United States, a second such occurrence known from this unit. Fossil steinkerns of tiny brachiopods, echinoid spines and ophiuroids are fluorapatite, with scarce phosphatic internal moulds of bivalves and two replaced ostracods. In contrast, the crinoid ossicles, almost all of which are >1000 µm, are preserved as stereomic moulds of silica or dolomite. Though the style of preservation is similar to another Virgin Limestone small shelly fossils-style assemblage, this assemblage preserves greater diversity, likely reflecting the variation in palaeocommunities across the shelf. The size selectivity of phosphatization is clear, as the majority of the fossils <1000 µm are phosphatized. Importantly, the original skeletal material does not exert the strongest control on style of preservation: crinoid ossicles are replaced or moulded by silica whilst ophiuroid and echinoid fragments are phosphatized. It is likely that the underlying phosphatization mechanisms are related to the small particle size of the skeletons or skeletal elements coupled with the local pore water environment. Early Triassic equatorial seas characterized by warm temperatures and lower oxygen levels likely fostered small shelly fossil-style preservation across the shelf during this time.

Numerical study on biogeochemical processes induced by methane leakage and its application in estimating the time of cold seeps formation

In shallow marine sediments, cold seeps of methane fluid is a widely observed phenomenon, which will lead to a series of biogeochemical reactions. These processes will change the pore water environment and trigger the formation of authigenic minerals. In this study, based on the data from the site GC10 in the NE South China Sea, numerical simulation studies were conducted to investigate the relative biogeochemical processes induced by methane leakage. The results of simulations show that anaerobic methane oxidation is the dominant sulfate consuming process in methane leakage environment, and the typical sulfate-methane interface is indicative of methane leakage. The pore water chemistry conditions are closely related to methane flux. Methane flux was calibrated from GC10 site data, when methane leaks upwards at flux of 2.42 × 10−3 mmol cm−2 a−1, the simulation results fit well with measured data. Some kinetic parameters of related reaction were calibrated during the fitting process. The microbially-mediated reactions in methane leakage environment trigger the precipitation of authigenic minerals, such as calcite and pyrite, which can sometimes be used as indicators of the occurrence of hydrate reservoirs. Through simulating the change of sulfate concentrations along the vertical column, the model was also used to estimate duration of active cold seeps at the study site. The results showed that the methane leakage in GC10 has been going on at least 5600 years. This study provided a new method to the study of cold seeps activities, and was significant for future investigations on the biogeochemical processes above the hydrate reservoirs.

Investigating the molybdenum and uranium redox proxies in a modern shallow anoxic carbonate rich marine sediment setting of the Malo Jezero (Mljet Lakes, Adriatic Sea)

The molybdenum (Mo) and uranium (U) isotope compositions recorded in carbonate rich sediments are emerging as promising paleo-redox proxies. However, the effects of early diagenetic effects within the sediments on these isotope systems are not well constrained. We examined the Mo and U isotopic systematics in anoxic carbonate rich sediments in a semi enclosed karstic marine lake (Malo Jezero) of the Island of Mljet, Adriatic Sea.Measurements of water column redox behavior in the lake since the 1950s, have shown a transition from anoxic-sulfidic conditions in the deeper water column to more oxic conditions and anoxia refined to the sediment and pore-waters. A 50 cm long sediment core from the deepest part of the lake, show a transition from moderate to high authigenic Mo and U accumulation with depth, consistent with the changing lake redox environment in the past. In the deep euxinic part of the core, the authigenic Mo and U are isotopically lighter and heavier, respectively, than seawater, following similar systematics as observed in other modern euxinic basins, with high, but non-quantitative, Mo and U uptake into the sediments.Based on Bahamas bank carbonate sediments, it has been suggested that the 238U/235U ratio is ~+0.25‰ higher compared to seawater from the effects of early carbonate sediment diagenesis and this carbonate vs. seawater off-set is applicable to carbonate rich sediments across the geological past. The shallower part of lake sediment core was deposited under similar redox conditions as the Bahamas sediments, and these sediments show an average 238U/235U ratio +0.31 ± 0.01‰ (2SE) higher than seawater. Although the average 238U/235U ratios for these two carbonate rich settings are similar, caution is necessary when inferring seawater 238U/235U compositions from such sediments, as they contain U from different sources (e.g. diagenetic uptake and carbonate-bound). The Mo isotope compositions within the same Malo Jezero sediments are variable but approaches the seawater composition at low pore-water H2S concentrations. This show the potential of using the Mo isotope composition from carbonate rich sediments to infer the seawater composition, however, further work is required to establish the link between the Mo isotope composition and the chemistry of the pore water environment.