Sulfate Reduction Research Articles

Kinetics of In-Situ Calcium Magnesium Carbonate Precipitation and the Need for Desulfation in Seawater-Flooded Carbonate Reservoirs

Summary Mixing of incompatible injection and formation brines leads to the deposition of inorganic sulfate scales such as barite, celestite, and anhydrite in and around production wells. This process is well documented in seawater-flooded clastic reservoirs. One technique to avoid the resulting formation damage is to remove sulfate from seawater before injection using nanofiltration; however, this process is costly. We identify in this paper that it may not always be necessary in higher-temperature carbonate reservoirs. In this paper, we describe the use of reactive transport reservoir simulation to investigate the impact of carbon dioxide (CO2) partitioning and changes in pH, ionic concentrations, and temperature on carbonate reactivity and the sulfate scaling risk in waterflooded carbonate reservoirs. Dissolution and precipitation of calcite, dolomite, gypsum, anhydrite, barite, and celestite are all modeled and found to be coupled through (various) common ion effects. The produced brine compositions are used to calculate the saturation ratios (SRs) and mass of precipitate that may form in the production system. Sensitivity to mineral reaction kinetics, particularly for the dolomite reactions, is accounted for. Results identify that there is a strong relationship between calcite dissolution and dolomite (or other calcium/magnesium carbonate mineral) precipitation reactions, which drive each other and are affected by the availability of CO2 in the residual oil phase. This evolves over time, and as the thermal front propagates, impacts the concentration of calcium and magnesium in the brines traversing the reservoir. Temperature changes around the injection wellbore impact CO2 and mineral solubilities. The concentration of calcium in the displaced brine mix is thus determined more by contact with rock and temperature than by mixing between injection and formation brines. Depending on location relative to the thermal front, this may lead to gypsum or anhydrite precipitation, thereby stripping sulfate out of the injection brine. Thus, the sulfate scaling risk at the production wells is significantly reduced by this sulfate depletion process: The sulfate is stripped out of the seawater as it warms up in the reservoir before it mixes extensively with the formation water and significantly before any mixture of the two brines reaches the production zone. Thus, any loss of permeability is restricted to deep within the reservoir, where the pore volume (PV) that can accommodate mineral precipitation is very large. In this work, we identify that for carbonate reservoirs above 90–100°C, stripping of sulfate due to coupled mineral reactions may reduce or eliminate the need for use of a sulfate reduction plant (SRP). The process is modeled for the first time, accounting for the impact of CO2 partitioning and thermal front propagation. Knowledge of the kinetics of calcium/magnesium carbonate precipitation is shown to be critical in predicting the extent of sulfate depletion.

Primary to post-depositional microbial controls on the stable and clumped isotope record of shoreline sediments at Fayetteville Green Lake.

Lacustrine carbonates are a powerful archive of paleoenvironmental information but are susceptible to post-depositional alteration. Microbial metabolisms can drive such alteration by changing carbonate saturation insitu, thereby driving dissolution or precipitation. The net impact these microbial processes have on the primary δ18O, δ13C, and Δ47 values of lacustrine carbonate is not fully known. We studied the evolution of microbial community structure and the porewater and sediment geochemistry in the upper ~30 cm of sediment from two shoreline sites at Green Lake, Fayetteville, NY over 2 years of seasonal sampling. We linked seasonal and depth-based changes of porewater carbonate chemistry to microbial community composition, insitu carbon cycling (using δ13C values of carbonate, dissolved inorganic carbon (DIC), and organic matter), and dominant allochems and facies. We interpret that microbial processes are a dominant control on carbon cycling within the sediment, affecting porewater DIC, aqueous carbon chemistry, and carbonate carbon and clumped isotope geochemistry. Across all seasons and sites, microbial organic matter remineralization lowers the δ13C of the porewater DIC. Elevated carbonate saturation states in the sediment porewaters (Ω > 3) were attributed to microbes from groups capable of sulfate reduction, which were abundant in the sediment below 5 cm depth. The nearshore carbonate sediments at Green Lake are mainly composed of microbialite intraclasts/oncoids, charophytes, larger calcite crystals, and authigenic micrite-each with a different origin. Authigenic micrite is interpreted to have precipitated insitu from the supersaturated porewaters from microbial metabolism. The stable carbon isotope values (δ13Ccarb) and clumped isotope values (Δ47) of bulk carbonate sediments from the same depth horizons and site varied depending on both the sampling season and the specific location within a site, indicating localized (μm to mm) controls on carbon and clumped isotope values. Our results suggest that biological processes are a dominant control on carbon chemistry within the sedimentary subsurface of the shorelines of Green Lake, from actively forming microbialites to pore space organic matter remineralization and micrite authigenesis. A combination of biological activity, hydrologic balance, and allochem composition of the sediments set the stable carbon, oxygen, and clumped isotope signals preserved by the Green Lake carbonate sediments.

Microbial Mobilization and Reprecipitation of Transition Metals in Waste Rock from an Abandoned Pyrite Mine: Implications for Metal Recovery

Abstract The Pyrite Mines in Sulphide, Ontario are a collection of historic mine workings representing one of more than 6000 abandoned mines in Ontario. Historic mines are receiving renewed interest as potential sources of critical minerals for use in low carbon technologies. This study characterizes waste rock from the Pyrite Mines in the context of metal distribution, microbial activity, bioleaching, and acid mine drainage (AMD) bioremediation for the recovery of metals. Acidophilic Fe-oxidizing bacteria cultured from the waste rock produced schwertmannite [Fe8O8(OH)8−2x(SO4)x·nH2O] and ammoniojarosite [NH4Fe3(SO4)2(OH)6] with similar morphologies to those often observed in acidic sulfidic mine settings. Fe- and S-oxidizing bacteria found naturally in the waste rock were used in waste rock bioleaching column experiments that demonstrated AMD formation and metal mobilization. The columns produced acidic leachates (pH = 1.75) containing dissolved constituents, including sulfur (1577 mg/L), iron (547.7 mg/L), nickel (12.6 mg/L), manganese (7.3 mg/L), copper (2.3 mg/L), zinc (2.0 mg/L), chromium (1.5 mg/L), and titanium (0.7 mg/L). The proportion of metals successfully leached from the waste rock was variable, with leaching efficiencies calculated for nickel (31%), manganese (10.5%), iron (1.5%), chromium (1.4%), and titanium (0.02%). The leachates produced by the bioleaching columns were amended in subsequent bioremediation columns using sulfate reducing bacteria cultured from the mine site. Remediation efficiencies for elements of interest were calculated as cobalt (100%), chromium (100%), copper (100%), iron (90%), titanium (68%), nickel (52%), manganese (52%), and sulfur (43%). Mapping elemental distributions in thin sections from one of the bioleaching columns using synchrotron X-ray fluorescence microscopy revealed the heterogeneity of the waste rock. Iron was observed in both euhedral mineral grains, likely pyrite, and in secondary cements coating grains in the waste rock. Nickel, manganese, and chromium were primarily co-located with the iron. Titanium was primarily co-located with calcium in titanite (CaTiSiO5), making it challenging to target with bioleaching. This study demonstrates the heterogeneous nature of metal distribution in waste rock from this historic mine site. It indicates that successful metal recovery from legacy mine waste will require such materials to be treated as anthropogenic mineral deposits that require “exploration” and characterization much like naturally occurring ore deposits.

Multicellular magnetotactic bacteria are genetically heterogeneous consortia with metabolically differentiated cells.

Consortia of multicellular magnetotactic bacteria (MMB) are currently the only known example of bacteria without a unicellular stage in their life cycle. Because of their recalcitrance to cultivation, most previous studies of MMB have been limited to microscopic observations. To study the biology of these unique organisms in more detail, we use multiple culture-independent approaches to analyze the genomics and physiology of MMB consortia at single-cell resolution. We separately sequenced the metagenomes of 22 individual MMB consortia, representing 8 new species, and quantified the genetic diversity within each MMB consortium. This revealed that, counter to conventional views, cells within MMB consortia are not clonal. Single consortia metagenomes were then used to reconstruct the species-specific metabolic potential and infer the physiological capabilities of MMB. To validate genomic predictions, we performed stable isotope probing (SIP) experiments and interrogated MMB consortia using fluorescence in situ hybridization (FISH) combined with nanoscale secondary ion mass spectrometry (NanoSIMS). By coupling FISH with bioorthogonal noncanonical amino acid tagging (BONCAT), we explored their in situ activity as well as variation of protein synthesis within cells. We demonstrate that MMB consortia are mixotrophic sulfate reducers and that they exhibit metabolic differentiation between individual cells, suggesting that MMB consortia are more complex than previously thought. These findings expand our understanding of MMB diversity, ecology, genomics, and physiology, as well as offer insights into the mechanisms underpinning the multicellular nature of their unique lifestyle.

Influence of riboflavin on the corrosion of X80 pipeline steel by Sulfate reducing bacteria

The sulfate reducing bacteria(SRB) is commonly attached to the surface of buried pipeline steel, and the electron shuttle in the corrosion medium can promote the release of electrons from iron oxidation through the bacterial cell wall into the cytoplasm to accelerate the corrosion of anode iron. This study investigated the impact of riboflavin (RF) as an endogenous electron shuttle on the corrosion behavior of X80 pipeline steel in SRB system. The findings indicated that while the type of corrosion products remains unchanged in samples under SRB+10 mg l−1 RF system, there was an expansion in both area and depth of corrosion pits on the sample surface, resulting in a corrosion loss rate approximately 3 times higher than that observed in SRB system. Furthermore, the polarization resistance (Rp) value of the sample in SRB system is about 2 ∼ 5 times that of the sample in SRB+10 mg l−1 RF system. Additionally, the corrosion current density of X80 pipeline steel samples soaked in SRB and SRB +10 mg l−1 RF system for 14 days is 9.31 × 10-6 A·cm−2 and 1.28 × 10−5 A·cm−2, and the addition of 10 mg l−1 RF increases the corrosion current density of SRB system by about 37.49%. These results indicated that the reaction resistance of SRB-induced MIC in X80 pipeline steel was significantly reduced due to the presence of RF.

Dual clumped isotopes (Δ47 and Δ48) reveal non-equilibrium formation of freshwater cements

Low-Mg calcite, precipitating from meteoric fluids, is a common mineral that forms in a variety of near-surface diagenetic environments. However, recent studies, based on a combination of analyses of δ18O and Δ47 values, have suggested that this mineral might form in disequilibrium and consequently yield kinetic bias in Δ47-derived temperatures and fluid δ18O values. Here, we use dual clumped isotope proxies (Δ47 and Δ48) to investigate the influence of kinetic isotope effects within different meteoric diagenetic zones of Holocene and Pleistocene carbonates from the southern Florida and the Dominican Republic. In the Miami Oolite, the primary aragonite ooids and secondary low-Mg calcite cements in the bulk sample were separated from each other and their isotopic compositions (δ13C, δ18O, Δ47 and Δ48 values) were measured. The Δ47 and Δ48 values of the separated aragonite are consistent with the modern ooid sediments and in approximate equilibrium with the surface seawater. In contrast, the low-Mg calcite cement shows the higher Δ48 and lower Δ47 values, than expected, with the disequilibrium arising as a result of CO2 degassing in the vadose zone. Such deviations of Δ47 and Δ48 values are also observed in low-Mg calcite vadose cements in the Dominican Republic. While low-Mg calcites formed in the lower freshwater phreatic zone in the Dominican Republic have the Δ47- and Δ48-derived temperatures close to expected, the same mineral forming near the water-table and upper phreatic zone shows much higher Δ48-derived temperatures (up to ∼ 90 °C). The possible origin of such elevated temperatures can be attributed to non-equilibrium processes caused by changes in pH and pCO2, mediated by microbial sulfate reduction. Such differential kinetic behavior of Δ48 values between vadose and phreatic zones could be used as a proxy marker for the presence and the location of a water-table. This study demonstrates the great potential of dual clumped isotopes in the investigation of meteoric diagenesis and will help understand the alteration of ancient sequences and the interpretation of stable C isotope trends that they contain.

Metagenomic evidence of a novel anammox community in a cold aquifer with high nitrogen pollution

The process of anaerobic ammonium oxidation by nitrite (anammox) is a globally essential part of N cycle. To date, 8 Candidatus genera and more than 22 species of anammox bacteria have been discovered in various anthropogenic and natural habitats, including nitrogen-polluted aquifers. In this work, anammox bacteria were detected for the first time in the groundwater ecosystem with high anthropogenic nitrogen pollution (up to 1760 mg NO3−-N/L and 280 mg NH4+-N/L) and low year-round temperature (7–8 °C) in the zone of a uranium sludge repository. Further metagenomic analysis resulted in retrieval of metagenome-assembled genomes of 4 distinct anammox bacteria: a new genus named Ca. Frigussubterria, new species in Ca. Kuenenia, and two strains of a new species in Ca. Scalindua. Analysis of the genomes revealed essential genes involved in anammox metabolism. Both strains of Ca. Scalindua chemeplantae had a high copy number of genes encoding the cold shock proteins CspA/B, which can also function as an antifreeze protein (CspB). Ca. Kuenenia glazoviensis and Ca. Frigussubterria udmurtiae were abundant in less N-polluted site, while Ca. Scalindua chemeplantae inhabited both sites. Genes for urea utilization, reduction of insoluble Fe2O3 or MnO2, assimilatory sulfate reduction, reactive oxygen detoxification, nitrate reduction to ammonium, and putatively arsenate respiration were found. These findings enrich knowledge of the functional and phylogenetic diversity of anammox bacteria and improve understanding of the nitrogen cycle in polluted aquifers.

Barite Replacement as a Key Factor in the Genesis of Sediment-Hosted Zn-Pb±Ba and Barite-Sulfide Deposits: Ore Fluids and Isotope (S and Sr) Signatures from Sediment-Hosted Zn-Pb±Ba Deposits of Iran

Iran hosts more than 350 Precambrian to Cenozoic sediment-hosted Zn-Pb±Ba and barite-sulfide deposits, including shale-hosted massive sulfide (SHMS, also called SEDEX) and Irish-type and Mississippi Valley-type (MVT) mineralization, and barite is a common mineral in these deposits. In the SHMS deposits, barite is typically found as fine-grained disseminations in thin laminae. In these deposits, the sulfide laminae often occur as diagenetic replacements and as bands containing authigenic and diagenetic barite and pyrite framboids. In the Irish-type Zn-Pb-Ba and stratabound barite-sulfide deposits, barite exhibits various textures, including fine-grained disseminated barite, banded zebra textures, veins, and massive barite lenses. In some of the giant Irish-type deposits, as well as in the stratabound barite-sulfide mineralization, the main stratabound sulfide ore is developed within a barite envelope and is characterized by the replacement of barite and pyrite by chalcopyrite, galena, and sphalerite. In the MVT deposits, the formation of barite is often related to dolomitization, and sulfide mineralization involves the replacement of the dolomitized carbonate rocks, as well as associated barite. Fluid inclusion studies on the Irish-type deposits indicate that the temperatures and salinities of the sulfide-forming fluids are higher compared to those of the barite-forming fluids. Fluid inclusion analyses of coarse-grained barites from Irish and MVT deposits reveal their hydrothermal origin. The δ3⁴S values of sulfide minerals (pyrite, sphalerite, and galena) in Irish-type deposits exhibit a broad range of low values (mostly −28 to +5‰), primarily revealing a process of bacterial sulfate reduction (BSR). However, the textures (replacement, colloform, and banded) and more positive sulfur isotope values (+1 to +36‰) in the SHMS Zn-Pb deposits suggest that bacterial sulfate reduction (BSR) plays a less significant role. We suggest that thermochemical sulfate reduction (TSR) connected to the direct replacement of barite plays a more relevant role in providing sulfur for the sulfide mineralization in the SHMS, barite-sulfide, and MVT deposits. Based on the textual evidence, sulfur isotopic data, and fluid inclusion studies, barite has been identified as a key controller for the subsequent Zn-Pb mineralization by providing a suitable host and significant sulfur contribution in the sediment-hosted Zn-Pb and stratabound barite-sulfide deposits. This implies that diagenetic barite might be a precursor to all types of sediment-hosted Zn-Pb mineralization.

Living in mangroves: a syntrophic scenario unveiling a resourceful microbiome

BackgroundMangroves are complex and dynamic coastal ecosystems under frequent fluctuations in physicochemical conditions related to the tidal regime. The frequent variation in organic matter concentration, nutrients, and oxygen availability, among other factors, drives the microbial community composition, favoring syntrophic populations harboring a rich and diverse, stress-driven metabolism. Mangroves are known for their carbon sequestration capability, and their complex and integrated metabolic activity is essential to global biogeochemical cycling. Here, we present a metabolic reconstruction based on the genomic functional capability and flux profile between sympatric MAGs co-assembled from a tropical restored mangrove.ResultsEleven MAGs were assigned to six Bacteria phyla, all distantly related to the available reference genomes. The metabolic reconstruction showed several potential coupling points and shortcuts between complementary routes and predicted syntrophic interactions. Two metabolic scenarios were drawn: a heterotrophic scenario with plenty of carbon sources and an autotrophic scenario with limited carbon sources or under inhibitory conditions. The sulfur cycle was dominant over methane and the major pathways identified were acetate oxidation coupled to sulfate reduction, heterotrophic acetogenesis coupled to carbohydrate catabolism, ethanol production and carbon fixation. Interestingly, several gene sets and metabolic routes similar to those described for wastewater and organic effluent treatment processes were identified.ConclusionThe mangrove microbial community metabolic reconstruction reflected the flexibility required to survive in fluctuating environments as the microhabitats created by the tidal regime in mangrove sediments. The metabolic components related to wastewater and organic effluent treatment processes identified strongly suggest that mangrove microbial communities could represent a resourceful microbial model for biotechnological applications that occur naturally in the environment.

Microbial Sulfate Reduction and Its Role in Carbon Sequestration in Marine Sediments

Microbial Sulfate Reduction and Its Role in Carbon Sequestration in Marine Sediments

Diagenetic archives of the deeply-buried Cambrian Xiaoerbulake Formation microbialite reservoirs, Bachu-Tazhong area, Tarim Basin, China

The deep-burial Cambrian Xiaoerbulake Formation microbialites reservoir hosts significant hydrocarbon in the Tarim Basin. However, limited understandings of fluid-rock interactions from deposition to deep-burial regimes hamper petroleum exploration. Here, petrological observations, in-situ elemental contents and porosity-permeability analyses were performed to understand the complex interactions and the microbialites performance. Dolo-mudstone, crystalline dolostone, and four kinds of microbialites are distinguished as dolostones types. In the depositional stage, microbialites are characterized by (evaporated) seawater dolomitization with the mediation of microbial activity. The dolostone matrix shows seawater-like δ13C, δ18O and REY patterns. Thrombolitic and foam spongy dolostones from high-energy subtidal to intertidal zones show large framework pores compared to stratiform stromatolitic dolostones from low-energy intertidal zones. In near-surface settings, meteoric diagenesis generates secondary pores, while fine-crystalline dolomite cements partially fill pores. During the shallow to intermediate burial regimes, medium-to coarse-crystalline dolomite cements yield negative δ18O values and slightly flat REY patterns. The precipitation of this dolomite phase further decreases reservoir porosity. In deep burial settings, one type of saddle dolomite is likely to be formed by replacement from carbonate precursors, while the second type might be directly precipitated from hydrothermal fluids. These two types of saddle dolomites show different cathodoluminescent characteristics and geochemical data. Subsequently, two types of calcite cements are formed by the calcification of dolomite and yield significant negative δ13C values due to thermochemical sulfate reduction. Finally, the third calcite phase is likely to be a direct precipitate from burial brines. Hydrothermal activity and thermochemical sulfate reduction generate and/or re-distribute secondary pores. Based on the plethora of depositional environments and fluid-rock interactions, thrombolitic dolostone generally yields higher porosity-permeability than other types of microbialites. Thrombolite reservoir has high potential for petroleum exploration and is significant for those concerned with microbialite hydrocarbon fields.

At Shores of a Vanishing Sea: Microbial Communities of Aral and Southern Aral Sea Region

Since the early 60s of the 20th century, as a result of agricultural development in the irrigated areas of Uzbekistan, the area of the Aral Sea has decreased by 90%, while the water salinity has increased from 1% to 20%. The aim of our work was to investigate the diversity of microbial communities of water and sediments of the Western Aral Sea, as well as of the adjacent soils and reservoirs using high-throughput sequencing of the 16S rRNA genes variable V4 region. It was found that the Aral Sea water with a salinity of 22% was dominated by uncultured Archaea of the family Haloferacaceae (22‒43%), as well as by bacteria of the genera Spiribacter and Psychroflexus. In the Aral Sea sediments the share of archaea was much lower (2‒17%), and among them the uncultured Woesearchaeales predominated. Among bacteria, dominating in Aral sediments, there were sulfate reducers of the phylum ‘Desulfobacterota’, as well as representatives of the genera Fusibacter, Halanaerobium, Guyparkeria, Marinobacter, Idiomarina and Thiomicrospira. In soil samples of the former Aral Sea bed with salinity of 8.2%, a variety of archaea of the phylum Halobacterota were present, as well as uncultured bacteria of the family Nitrosococcaceae. However, in the rhizosphere of Ewresmann’s teresken plant (Kraschennininikovia ewresmanniana) growing there, archaea accounted for only 4% and mainly represented the family Nitrososphearaceae. 33% of all prokaryotes in the rhizosphere microbiome were the uncultured representatives of the phylum Actinomycetota. The microbial community of the teresken rhizosphere turned out to be similar to the microbial communities of the soil of the Ustyurt plateau, located in 3 km from the Aral Sea shore. The fresh water flowing along the former Aral Sea bed from an artificially drilled well also causes significant changes in the microbial communities: cyanobacterial mats and associated organotrophic bacteria develop along the stream bed with the increasing salinity (0.5‒2%). Finally, the greatest diversity of prokaryotes was found in the microbial community of Sudochie Lake sediment with salinity of 1%, which is probably a modern analogue of the Aral Sea microbiome before its shallowing.

Sulfidation of Cd-Sch during the microbial sulfate reduction: Nanoscale redistribution of Cd

Schwertmannite (Sch) is found in environments abundant in iron and sulfate. Microorganisms that utilize iron or sulfate can induce the phase transition of Schwertmannite, consequently leading to the redistribution of coexisting pollutants. However, the impact of the molar ratio of sulfate to iron (S/Fe) on the microbial-mediated transformation of Schwertmannite and its implications for the fate of cadmium (Cd) have not been elucidated. In this study, we examined how S/Fe influenced mineral transformation and the fate of Cd during microbial reduction of Cd-loaded Schwertmannite by Desulfovibrio vulgaris. Our findings revealed that an increase in the S/Fe ratio facilitated sulfate-reducing bacteria (SRB) in mitigating the toxicity of Cd, thereby expediting the generation of sulfide (S(-II)) and subsequently triggering mineral phase transformation. As the S/Fe ratio increased, the predominant minerals in the system transitioned from prismatic-cluster vivianite to rose-shaped mackinawite. The Cd phase and distribution underwent corresponding alterations. Cd primarily existed in its oxidizable state, with its distribution being directly linked not only to FeS content but also showing a robust correlation with phosphorus. The coexistence of vivianite and FeS minerals proved to be more favorable for Cd immobilization. These findings have significant implications for understanding the biogeochemistry of iron (oxyhydr)oxides and Cd fate in anaerobic environments.

Differential fault-fluid alterations and reservoir properties in ultra-deep carbonates in the Tarim Basin, NW China

The development of high-quality carbonate hydrocarbon reservoirs in the ultra-deep (7000–10000 m) Lower Paleozoic strata of the Tarim Basin was substantially related to tectonic evolution, strike-slip faults, and diagenetic fluids. Detailed studies of the influences of tectonic evolution and strike-slip faults on the properties of diagenetic fluids and the development mechanisms of ultradeep carbonate reservoirs under the control of both faults and fluids are required to identify high quality reservoirs. In this study, end-member geochemical indicators of meteoric water, hydrothermal fluid, and formation fluid were constructed based on typical diagenetic mineral and geochemical data obtained from representative wells. Meteoric karst associated with strong tectonic uplift was the main diagenetic event along strike-slip faults in the Tahe area. The Shunbei area was generally affected by buried formation water, and locally by weak meteoric water or hydrothermal fluids. The Tazhong, Shunnan, and Gucheng areas were predominantly affected by strong hydrothermal fluids along strike-slip faults associated with strong volcanic activity, while some wells, such as TZ12, reveal the influence of thermochemical sulfate reduction (TSR). Differences in fault fluid types and properties resulted in differential development of ultra-deep carbonate reservoirs among the different areas. In the Tahe area, meteoric water alteration along faults formed karst fracture-cavity reservoirs. In the Shunbei area, fault-cavity carbonate reservoirs were formed by strong strike-slip faults, whereas fluid alteration was weak. Hydrothermal dissolution reservoir in the Tazhong area, hydrothermal silicification reservoir in the Shunnan area, and hydrothermal dolomitization reservoir in the Gucheng area are developed, respectively.

Biochemically induced diagenesis of Jurassic micrite: evidence from phase analysis, carbon, oxygen, and strontium isotopes (Franconian Alb, Germany)

The marine Upper Jurassic rocks of the Franconian Alb consist largely of micritic carbonate of partly dolomitized reef mounds and bedded basinal limestone. All carbonates were lithified in the shallow (centimeters, meters) subsurface and have a wide range of ∂13C (≤ + 3‰ to − 10‰VPDB) but always negative ∂18O (− 1 to − 6‰VPDB). Dolomite and reef limestone show the highest ∂18O and ∂13C values. The most negative ∂13C (≥ − 10‰) occurs mainly as cement in dolomite of a basinal, partly dolomitic, biostrome interval. Basinal limestone shows intermediate ∂13C values. Because freshwater diagenesis and elevated temperatures cannot explain the observed isotope values, pH is here considered a major factor influencing the isotope signal of micritic limestone. The bulk sediment isotope signal was reset to lower values, from an original lime mud with ∂13C ≥ 3‰ and a ∂18O of ≥ + 1‰, as a result of biochemically induced diagenesis. Carbonate, probably mostly aragonite but occasionally including dolomite, was dissolved in a zone where low pH developed as a result of organic matter degradation. Dissolved carbonate was translocated by diffusion and re-precipitated as cement (ca. 50vol%) in a zone with elevated pH where all in situ lime mud ∂18O was reset. Imported cement carbonate precipitated in equilibrium with the pore fluid with negative isotope values, whereas ∂13C of the in situ lime mud remained unmodified. The negative shift of the bulk ∂13C and ∂18O is variable and depends on pH and the contribution of 12C from anaerobic sulfate reduction in the zone of cement precipitation. This produced an ubiquitous covariance of ∂18O and ∂13C. Incorporation of seawater-derived Mg2+ during recrystallization of carbonate can account for the local dolomitization. Elevated 87Sr/86Sr ratios are explained as a result of interaction of clay minerals with the stationary pore fluids. This study shows that the isotopic signal produced by biochemically induced shallow submarine subsurface carbonate diagenesis can be indistinguishable from freshwater diagenesis, that ∂18O and ∂13C of the bulk rock are always reset, and that carbonates can show, in the presence of clay minerals, elevated 87Sr/86Sr ratios even when the pore fluids were never exchanged.Graphical

Corrosion behavior of X60 pipeline steel in the presence of Sulfate Reducing Bacteria cultured in seawater and mud from the East China Sea

Sulfate-reducing Bacteria (SRB) corrosion is a serious threat to the safety of marine pipelines.To reveal the influence of the corrosion behavior of X60 pipeline steel in the presence of SRB cultured in seawater and mud from the East China Sea The corrosion behavior of X60 pipeline steel was studied with weight loss measurements, microstructure and membrane composition analysis, electrochemical measurements The corrosion rate in sterile seawater is 0.11 mm/y, whereas, in SRB-infested seawater, it increases by 245 % to 0.38 mm/y. In sterile sea mud, the corrosion rate is 0.15 mm/y, but in SRB-infested sea mud, it increases by 87 % to 0.28 mm/y. In the corrosive environment of seawater and mud in the East China Sea, SRB significantly accelerates the microbial corrosion of X60 pipeline steel. These findings provide theoretical guidance for further research on SRB corrosion mechanisms and corrosion control of marine pipelines.

Thermophilic fermentation of sugarcane vinasse: Process flexibility explained through characterizing microbial community and predicting metabolic functions

This study unravels some of the complex microbial interactions established in the fermentation of sugarcane vinasse. The microbial communities of four thermophilic (55 °C) fixed-bed vinasse-fed reactors were analyzed by 16S rRNA gene amplicon sequencing and the marker gene data were aligned with reference genomes to predict metabolic functions of the microorganisms. The production (by Lactobacillus) and utilization (mainly by Thermoanaerobacterium and Caproiciproducens) of lactate explain the primary pathways associated with substrate fermentation towards biohydrogen, whilst only a single genus (Desulfotomaculum) and very low abundances of the enzymes involved in sulfate reduction were found. Although the abundant microbes in the inocula failed to grow during the continuous operation in all reactors, these fermentative consortia behave like microbial pantries containing bacteria that will grow according to the operating conditions, shaping lactate-accumulating (pH < 5.0) or lactate-consuming (pH > 5.0) and eventually sulfate-reducing (pH > 6.0) microbial communities in vinasse thermophilic fermentation.

Ligand Basicity and Chelate Effects on Sulfur Insertion vs. Sulfur Reduction by Zinc Thiolate Complexes.

4- and 5-coordinate zinc thiolate complexes supported either by bis(carboxamide)pyridine frameworks or by substituted tris(pyrazolyl)borate ligands react with elemental sulfur (S8) following two distinct pathways. Some zinc thiolate moieties insert sulfur atoms to form zinc polysulfanide complexes, while others reduce sulfur and oxidize the thiolate. Here, we compare the effects of ligand electronics, strain, and sterics for selecting the respective reaction pathway. These results show that chelating and electron-deficient thiolate ligands better stabilize persistent zinc-bound polysulfanide species.

Total alkalinity change: The perspective of phytoplankton stoichiometry

AbstractMany biogeochemical processes change total alkalinity: this has been reported for carbonate precipitation and dissolution, uptake and release of various nitrogen‐containing compounds, uptake of phosphate, sulfate reduction combined with methane oxidation. However, the list is not exhaustive. Here we discuss additional processes, namely the uptake of Mg, K, Ca by phytoplankton, and calculate their contribution based on the explicit conservative expression for TA and an extended (compared to Redfield's C : N : P) stoichiometry of phytoplankton. These additional contributions are of the same order of magnitude as that of phosphate uptake and thus much smaller than the contribution from nitrate uptake and of opposite sign to the contribution by nitrate and phosphate uptake.

Evaluation of functional characteristics of Acidithiobacillus thiooxidans microencapsulated in gum arabic by spray-drying as biotechnological tool in the mining industry.

The mining and metallurgical industry represents one of the leading causes of environmental pollution. In this context, the optimization of mineral waste management and the efficient extraction of metals of interest becomes an imperative priority for a sustainable future. Microorganisms such as Acidithiobacillus thiooxidans have represented a sustainable and economical alternative in recent years due to their capacity for environmental remediation in bioleaching processes because of their sulfur-oxidizing capacity and sulfuric acid generation. However, its use has been limited due to the reluctance of mine operators because of the constant reproduction of the bacterial culture in suitable media and the care that this entails. In this work, the central objective was to evaluate the functional characteristics of A. thiooxidans, microencapsulated and stored at room temperature for three years in vacuum bags, using a spray drying process with gum arabic as a wall vector. Growth kinetics showed a survival of 80 ± 0.52% after this long period of storage. Also, a qualitative fluorescence technique with a 5-cyano-2-3 ditolyl tetrazolium (CTC) marker was used to determine the respiratory activity of the microorganisms as soon as it was resuspended. On the other hand, the consumption of resuspended sulfur was evaluated to corroborate the correct metabolic functioning of the bacteria, with results of up to 50% sulfur reduction in 16 days and sulfate generation of 513.85 ± 0.4387 ppm and 524.15 ± 0.567 ppm for microencapsulated and non-microencapsulated cultures, respectively. These results demonstrate the success after three years of the microencapsulation process and give guidelines for its possible application in the mining-metallurgical industry.