Authigenic Carbonate Precipitation Research Articles

Provenance of mixed volcaniclastic-carbonaticlastic gravity-flow deposits: a case study from the Cretaceous of the southern Central Alborz (Iran)

ABSTRACT Understanding the petrographic and geochemical characteristics of different tectonic settings is essential to improving traditional methods of identifying the provenance of palaeo-sedimentary environments. This research focuses on the K2b unit, which consists of mixed carbonate and volcanic lithic sandstones located in Iran with the age of the Turonian-Early Campanian period. Five sedimentary lithotypes with distinct petrographic and geochemical signatures were identified in the Turonian/Lower Campanian K2b unit, which consists of coarse-grained fan-delta strata. Carbonate and volcanic lithic fragments are the most characteristic components of mostly quartzo-lithic to felspatho-litho-quartzose sandstone layers, documenting a unidirectional paleocurrent pattern with the north-eastward direction. The original composition has undergone diagenesis, resulting in the precipitation of authigenic carbonates and depleting Rare Earth Elements (REE) except for Eu, which shows a positive anomaly. The K2b fan delta was situated on the margin of the proto-south Caspian back-arc basin, and the sediments were sourced from the undissected magmatic arc. The gravity flow deposits in the K2b unit were likely triggered by tectonic activity in the catchment area of the fan delta, leading to uplift and formation of relief associated with the regional Mosha Fault and, on a larger palaeogeographic scale, with subduction of the Arabian plate beneath the Iranian plate during Turonian-Early Campanian.

Factors controlling long-term carbon sequestration in the paleo-Yellow River delta: Implications for future delta management

River deltas have contributed to the regulation of atmospheric CO2 concentrations throughout Earth's history, but the capacity and controlling factors for deltas to serve as permanent carbon sinks over the long term are unclear. To address this issue, we carried out a high-resolution assessment of carbon burial in a well-dated sediment core (BXZK13) from the paleo-Yellow River delta on the west coast of the Bohai Bay. We found that the sedimentary environments in core BXZK13 since the Late Pleistocene (∼84 k cal yr B.P.) were divided into seven depositional units. The apparent mass accumulation rate (AMAR) of total organic carbon (TOC) and total inorganic carbon (TIC) varied significantly between depositional units. The average rates were highest in delta front deposits (TOC: 135 g m−2 yr−1, TIC: 333 g m−2 yr−1). Notably, the rates of carbon accumulation were dominated by TIC. The differences in the characteristics of TIC in the borehole compare to those of carbonates in Yellow River sediments and the positive correlation between TIC and Fe suggested that authigenic carbonate contributed significantly to long-term carbon burial in the delta. The apparent sedimentation rate (ASR) dominated the variations of the carbon AMAR, and the high clay and Fe content in the sediment enhanced TOC preservation and authigenic carbonate precipitation. Low concentrations of TIC were associated with several cold events, and there was a positive correlation between the chemical index of alteration and TIC. The implication was that climate may have affected the dynamics of inorganic carbon burial by regulating authigenic carbonate precipitation. These results enable a more thorough understanding of the factors that control long-term carbon sequestration, which is critical for both management purposes as well as assessment of the role of deltas in past and future climate change.

Assessing biogeochemical controls on porewater dissolved inorganic carbon cycling in the gas hydrate-bearing sediments of the Makran accretionary wedge, Northeastern Arabian Sea off Pakistan

Quantitatively assessing the porewater dissolved inorganic carbon (DIC) cycling in methane-enriched marine sediments is crucial to understanding the contributions of different carbon sources to the global marine carbon pool. In this study, Makran accretionary wedge was divided into Zone 1 (high methane flux area) and Zone 2 (background area). Porewater geochemical compositions (Cl–, SO42–, NH4+, Mg2+, Ca2+, Ba2+, DIC and δ13C-DIC) and a reaction-transport model were used to determine the DIC source and calculate the DIC flux through carbonate precipitation and releasing into overlying seawater in sediments. Zone 1 is characterized by the shallower depth of sulfate-methane transition (SMT), where most of porewater sulfate was consumed by anaerobic oxidation of methane (AOM). In contrast, a relatively low flux of methane diffusion in Zone 2 results in a deeper SMT depth and shallow sulfate is predominantly consumed by organoclastic sulfate reduction (OSR). Based on the porewater geochemical profiles and δ13C mass balance, the proportions of porewater DIC originating from methane were calculated as 51% in Zone 1 and nearly 0% in Zone 2. An increase of porewater DIC concentration leads to authigenic carbonate precipitation. Solid total inorganic carbon (TIC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM) analysis display that carbonate content increases with depth and aragonite appears at or below the depths of SMT. Meanwhile, the flux of DIC released from sediments calculated by the reaction-transport model is 51.3 ~ 90.4 mmol/m2·yr in Zone 1, which is significantly higher than that in Zone 2 (22.4 mmol/m2·yr). This study demonstrates that AOM serves as the dominant biogeochemical process regulating the porewater DIC cycle, which has an important impact on the authigenic carbonate burial and the seawater carbonate chemistry.

The transition from normal marine to evaporitic conditions recorded in a cold seep environment: The Messinian succession of Northern Italy

Messinian pre-evaporitic seep carbonates outcropping in the Tuscan-Romagna area share a common upward stratigraphic trend: massive seep carbonates rich in large lucinids, modiolids and planktonic foraminifera pass upward to horizontally laminated carbonates free of macrofauna and foraminifera. A transitional macrofauna-free facies marks the passage in some sections, sometimes with faint lamination. Thin section petrography, SEM-EDS analyses, and X-ray diffraction revealed a high textural and mineralogical variability between the studied sections and facies. In general, the upward facies transition is associated with a switch from massive packstone/grainstone with complex carbonate mineralogy to laminated mudstone microfacies with monomineralic, mostly dolomitic, carbonate composition. The δ13C values of all facies indicate domination of methane-derived carbon, thus demonstrating a methane-charged sedimentary setting with precipitation of authigenic carbonates induced by anaerobic oxidation of methane. The transitional and laminated facies contain several structures typical of microbial sediments, such as peloids, filamentous features, clotted micrite, fibrous cement, and frequent fenestrae; web-like structures are remnants of cyanobacterial mats and resemble Entophysalidaceae thriving at the bottom of the Messinian sea. The distinctive depositional and biotic switch (abrupt disappearance of macrofauna and planktonic foraminifera, predominance of dolomite over calcite, absence of aragonite, presence of horizontal lamination) reflects important environmental changes taking place in the basin. The rise of δ18O from the massive, through transitional, to the laminated facies suggests either a drop of bottom-water temperature or an increase of salinity. Nevertheless, other paleoenvironmental changes must have co-occurred in order to account for the dramatic facies shift observed. We hypothesize that this change could reflect the development of water-column stratification with respect to both salinity and oxygen concentration shortly before the Messinian Salinity Crisis.

Authigenic Carbonate Precipitation at Yam Seep Controlled by Continuous Fracturing and Uplifting of Four‐Way Closure Ridge Offshore SW Taiwan

AbstractHydrocarbon seeps are common manifestations of gas leakage from the seafloor. However, the fate of methane seepage within the gas hydrate stability zone at active margins is poorly constrained. This study presents a 40‐thousand‐year record of hydrocarbon seepage archived by a ∼5‐m long core composed of authigenic carbonate from the Yam Seep area, Four‐Way Closure Ridge off SW Taiwan. Different carbonate microfacies could be distinguished: Consolidated microcrystalline aragonite representing lithified host sediments intercalated by pure aragonite present in 10–50 cm thick intervals in the core. These aragonite intervals are interpreted as having precipitated within former fractures in the host rock. High resolution U‐Th dating of these aragonites is interpreted to record the minimum age of the opening of these fractures. The chronology of aragonite precipitation throughout the core suggests a record of continuous seepage from ∼41 to 2 ka that fluctuated in intensity over this time period. The chronology of putative fracturing events and observed carbonate precipitation suggest (a) an active period of fracturing and seepage from ∼37 to 27 ka, (b) a more quiescent period from ∼27 to 16 ka, followed by (c) another active period from ∼16 to 12 ka. A schematic model illustrates the evolution of carbonate formation within the core influenced by faulting, fracturing, erosion, gas hydrate accumulation, and aragonite precipitation and provides a unique 40,000‐year‐old record of methane seepage and crucial insights into the dynamics of long‐term seepage systems at active margins.

Sediment flux and early diagenesis inferred from high-resolution XRF-CS data and iron and arsenic sulfides during the last 30 kyr in Lake Urmia, Iran: Implications for studies of hypersaline lakes

We analyzed by high resolution X-ray fluorescence core scanning (XRF-CS) the elemental composition of a 12.5 m long composite sediment core extracted from the hypersaline Lake Urmia (NW Iran). The main objective of the study was to reconstruct on a high temporal scale, the changes in sediment origin/inflow and water levels of Lake Urmia over the last 30,000 years. Combined with previously obtained results on 14C accelerated mass spectrometry (AMS) chronology, grain size and distribution of major minerals, albeit with a much lower temporal resolution than the XRF-CS data, this multi-proxy approach allowed recognition of specific hydrological changes and associated sedimentary processes in the Lake Urmia basin, including physical and chemical weathering, depositional fluxes and carbonate crystallization processes in lake water, and early diagenesis in anoxic bottom sediments. The high natural logarithm ratios (ln-ratios) of K/Ti, Ca/Ti and Sr/Ca, and low ln-ratios of Rb/Sr reveal increasing chemical weathering in the catchment area in conjunction with increasing authigenic carbonate precipitation in the lake. These findings reflect wet conditions, high lake levels and less saline water during the following intervals (i) 29.8–20.2, (ii) 15.2–13.3, (iii) 11.8–5.6 and (iv) 4.1–2.3 cal kBP. In contrast, the increasing ln-ratios of Rb/Sr associated with decreasing ln-ratios of K/Ti, Ca/Ti and Sr/Ca indicates enhanced erosion in the catchment area linked to drier conditions, lower lake levels and more saline conditions predominating at around 30–29.8 cal kBP, 20.2–15.2, 13.3–11.8, and 5.6–4.1 cal kBP. Based on the As-XRF-CS pattern and magnetic parameters we identified iron and naturally-occurring arsenic sulfides rarely reported from saline lakes, acting as specific indicators of anoxic conditions in the lake bottom environment. Moreover, XRF-CS data revealed short-lived periods with increasing chemical weathering in the catchment area at (i) 28.6–28.3, (ii) 27.3–27.1, (iii) 4.1–3.6 and (iv) 3.4–3.3 cal kBP, as well as increasing erosion at (i) 27.0–26.8, (ii) 26.3–26.0, (iii) 25.6–25.3 and (iv) 24.6–24.4 cal kBP. Overall, this study confirms the previously reported findings concerning the sediments of Lake Urmia as well as completing these, both by providing more details on the environment for the periods already identified and by highlighting events of short duration. In particular, the results reported here permit better definition of the processes of chemical weathering versus erosion in the catchment area, and of the oxygenation levels of the lake bottom. The close correlation of these long- and short-term changes with the North Atlantic climate system clearly indicates that the Lake Urmia area has been affected mainly by this system during the last 30 cal kBP.Over and above their value with regard to Lake Urmia, these new data fill an important gap in eastern Mediterranean/western Asia paleoclimate records as a whole, providing unique and continuous 30 cal kBP information on the possible driving mechanisms of the observed changes. These can be compared to existing data on paleoenvironmental and climatic changes on regional and global scales and can also be used in global circulation models.

Quantification of the sources of sedimentary organic carbon at methane seeps: A case study from the South China Sea

Large amounts of methane are stored along continental margins in the form of methane hydrate. Methane hydrate is sensitive to environmental change, resulting in the release of substantial quantities of methane upon its destabilization. In the marine subsurface, microorganisms consume most of the methane in the sulfate-methane transition zone and convert a certain amount of methane into organic matter. Burial of such organic matter deriving from methane oxidation represents a long-term carbon sink, therefore mitigating the effect of a prominent greenhouse gas on global warming. However, the controls on the formation and consumption of sedimentary organic matter at marine seeps remain poorly constrained, impeding accurate quantification of carbon burial at seeps and its role in the marine carbon cycle. To gain new insight on the effect of seeps on carbon burial, sediments from two seep sites of the South China Sea (Site F, Haiyang 4) and a nearby reference site (Jiulong canyon) were analyzed for total organic carbon contents (TOC), δ13CTOC and Δ14C values, total inorganic carbon contents (TIC) and δ13CTIC values, as well as organic nitrogen (N) contents. Depth distributions reveal that the TOC at seeps (Site F, 0.55% ± 0.08%, Haiyang 4, 0.67% ± 0.11%) is higher than in sediments not affected by seepage (Jiulong canyon, 0.50% ± 0.10%). The enrichment of total sulfur, high TIC, and negative δ13CTIC values in sediments from Site F and Haiyang 4 agrees with locally prominent sulfate-driven anaerobic oxidation of methane (AOM) and resultant precipitation of authigenic carbonate. At the two seep sites, the sediments are characterized by more negative δ13CTOC and Δ14C values and a lower TOC/N ratio, indicating a contribution of the microbial fixation of 13C-depleted methane to the local pool of sedimentary organic matter. A linear increase in 14C ages of organic carbon with sediment depth at the reference site indicates steady depositional conditions, whereas the 14C age of organic carbon at seeps is typified by contributions of methanotrophy-derived carbon. A Δ14C mass balance approach shows that carbon derived from fossil methane accounts for at least 10 to 20% of the organic carbon preserved in the sediments. By comparing seeps, hydrate-bearing sediments, modern coastal sediments, and Archaean rocks, it becomes apparent that the carbon stable isotope composition of organic carbon in seep sediments is mainly controlled by the rate of methane oxidation and marine primary productivity.

The role of anaerobic methane oxidation on the carbonate authigenesis in sediments of the subtropical Beibu Gulf, South China Sea: A reactive–transport modelling approach

The formation and burial of authigenic carbonate in marine sediment significantly affect the sedimentary carbon cycle and its isotopic mass balance in geological history. Anaerobic oxidation of methane (AOM) is the primary driver of authigenic carbonate precipitation within the sulfate-methane transition zone (SMTZ). Quantitative estimations of the role of AOM on the authigenic carbonate precipitation and its carbon isotope under non-steady-state processes (e.g., changes in methane fluxes at the bottom sediment, sedimentation rates or organic fluxes in the surface sediment), however, are still limited. In this study, we use geochemical data from porewater (e.g., the concentration of sulfate, calcium, magnesium, strontium, dissolved inorganic carbon, total alkalinity) and solid sediment (e.g., organic matter content, and carbonate content) in different depositional environments of the subtropical Beibu Gulf, South China Sea, combined with a diagenetic reactive-transport modelling approach, to estimate the mineralogy of authigenic carbonate, the relationship between AOM and authigenic carbonate precipitation, and the impact of AOM rate on carbon isotope of sediment carbonate (δ13CCar). The results show that high-Mg carbonates (high-Mg calcite and dolomite) are the main type of authigenic carbonate (∼80%) formed in the methane-bearing sediments, leading to higher porewater Sr2+/Ca2+ (>0.02) and Mg2+/Ca2+ (>20) within the SMTZ. Our modelling analysis highlights that the non-steady-state induced by increased methane flux from the underlying sediments can significantly accelerate the authigenic carbonates formation within the SMTZ. Using parametric sensitivity analysis, we observed that even a 1% increase in the authigenic carbonate fraction of sediment carbonates results in significant changes in δ13CCar within the SMTZ (from −1‰ to −2‰), mainly due to lighter carbon isotopes produced by more intensive AOM processes. Noteworthily, the terrestrial-to-marine transition was identified by the sediment and porewater geochemical profiles at site SO-8. Although lower authigenic carbonate precipitation occurs in terrestrial sedimentary environments, the proportion of authigenic carbonate in terrestrial environments (11%) is much higher than that in marine environments (1%), resulting in carbon isotopes of carbonate in terrestrial sediments becoming more negative (−5‰).

Volcanogenic aluminosilicate alteration drives formation of authigenic phases at the northern Hikurangi margin: Implications for subseafloor geochemical cycles

Alteration of volcanogenic aluminosilicates (VAs) in marine sediments is recognized as critical in regulating geochemical cycles and sustaining the oceanic deep biosphere, but rates of VA alteration and its associated authigenic mineral formation are not commonly reported. Here we present results on analyses of sediments and pore water recovered from the upper 150 mbsf of four sites drilled on the northern Hikurangi margin during IODP Expeditions 372 and 375. Petrographic analyses show that volcanogenic materials (glass shards, feldspar, volcanic lithoclasts) constitute important components (15–45 wt%) of the hemipelagic mud, and reveal ongoing glass alteration with accompanying authigenic phase formation. A reaction-transport model constrained by pore water Sr, 87Sr/86Sr, Ca, Mg, and Si was applied to simulate VA diagenetic reactions. Our model results yield VA alteration rates of 0.047–0.64 mmol Sr m−2 yr−1, with substantially higher values at Sites U1517 and U1520 that experienced rapid sediment emplacement. In addition, our simulations show that >99% of the dissolved Si generated by VA alteration is fixed in silica cement and authigenic clay, and that ∼50% of Ca incorporated in the authigenic carbonate is supplied by VA alteration. First-order estimates suggest that, in addition to authigenic carbonate precipitation, authigenic clay formation may represent an important sink for dissolved Mg. This study quantitatively examines the linkage between VA alteration and formation of authigenic phases, highlights its role in subsurface geochemical cycles, and indicates that slope instability may play an important role in promoting VA diagenesis.

Metalloenzyme signatures in authigenic carbonates from the Chukchi Borderlands in the western Arctic Ocean

Migration of methane-rich fluids at submarine cold seeps drives intense microbial activity and precipitation of authigenic carbonates. In this study, we analyzed microbially derived authigenic carbonate samples recently recovered from active gas hydrate mounds on the southwestern slope of the Chukchi Borderlands (CB), western Arctic Ocean. Our main aim was to characterize the distribution patterns of trace elements in carbonate-hosted lipid fractions to assess metalloenzyme requirements of microbes involved in anaerobic oxidation of methane (AOM). We measured stable isotopes, trace elements, lipid biomarkers, and genomic DNA, and results indicate the dominance of AOM-related lipid biomarkers in studied carbonate samples, as well as a predominant occurrence of the anaerobic methanotrophic archaea (ANME)-1. We also report evidence for significant preferential enrichments of various trace elements (Li, Ni, Co, Cu, Zn, and Mo) in the total lipid fractions of CB carbonates, relative to elemental compositions determined for corresponding carbonate fractions, which differ from those previously reported for other seep sites. We hypothesize that trace element enrichments in carbonate-hosted lipid fractions could vary depending on the type of AOM microbial assemblage. Additional work is required to further investigate the mechanisms of lipid-bound trace elements in cold seep carbonates as potential metalloenzymes in AOM.

Hydroclimatic variability in Northeast India during the last two millennia: Sedimentological and geochemical record from Shilloi Lake, Nagaland

The evolution of the monsoonal climate in the Indian Himalayan region remains poorly understood due to the sparse coverage of paleoclimatic datasets. In the present paper, elemental concentrations and grain size parameters are measured for a radiocarbon-dated sediment core retrieved from Shilloi Lake (Nagaland, India) to understand climate variability over north-eastern India during the past two thousand years. The end-member modeling of grain-size distribution along with the elemental composition and ratios (Mg/Al, Sr/Al, Ti/Al) are used to identify changes in clastic input and authigenic carbonate precipitation as well as lake level changes. In addition, the REE distribution pattern and elemental ratios (U/Th, Europium anomaly – Eu*) are evaluated to understand provenance and redox conditions. We identify two main hydrological events: (i) wet conditions during ~1900 to ~1000 cal yrs. BP characterised by high clastic sediment input (as indicated by increased Mg, Al, Mg/Al) and dominant contribution of fine-grained sediments as represented by end member (EM) 1 in zone 1, and (ii) an increase in aridity as signified by decreasing detrital content and increased coarse-grained sediments (EM3) in zone 2 (~1000 cal yrs. BP to present). The regional comparison of paleoclimatic records from NE Himalaya and central India shows an opposing trend in precipitation patterns. However, a synthesis of hydrological proxy records from the tropical Pacific region does not point to an active role of ENSO in the study region. Comparative analysis of modern precipitation data and paleo-records shows that the opposing behaviour resembles an “active-break” pattern that produces an east-west precipitation dipole in central and northeast India.

Pore-Water Geochemical Gradients of Sulfate, Calcium, Magnesium, and Iodide Correlated With Underlying Gas Hydrate Potential: A Case Study of the Shenhu Area, South China Sea

Geochemical profiles in pore water of marine sediments have been considered as, important indicators of gas hydrate occurrence. In the gas hydrate area around the world, the decrease of sulfate, calcium, and magnesium concentrations with depth mainly results directly or indirectly from the anaerobic oxidation of methane (AOM). The ubiquitous abnormally high concentration gradients of iodide in the research area reflect the large methane-generating potential of the area. Thus, we explore the feasibility of using gradients of sulfate, iodide, and authigenic carbonate precipitation as indicators for gas hydrate in the regional exploration of gas hydrate formation. We test the criterion in the gas hydrate zone in the South China Sea (SCS) for the recognition of gas hydrate by using the gradients of sulfate, calcium plus magnesium, and iodide. Contour maps of pore-water gradients from expeditions in the study area are used to correlate the key gradients to underlying gas hydrate occurrence. The results show that the largest potential gas hydrate indicated by the contour maps of the indicators are well consistent with the discovery of GMGS1 and GMGS3 expedition. It implies the possible applicability of this geochemical method in gas hydrate exploration. Also, we identify a promising area in the South China Sea for future gas hydrate investigations. It is the first collective application of the gradients of sulfate, calcium plus magnesium, and iodide to a gas hydrate terrane, especially to a large area of the SCS. We believe that the result of this research will benefit the future exploration of gas hydrate and will arouse a lot of interest from other researchers.

Benthic Organic Matter Transformation Drives pH and Carbonate Chemistry in Arctic Marine Sediments

AbstractCarbonate chemistry of the Arctic Ocean seafloor and its vulnerability to ocean acidification remains poorly explored. This limits our ability to quantify how biogeochemical processes and bottom water conditions shape sedimentary carbonate chemistry, and to predict how climate change may affect such biogeochemical processes at the Arctic Ocean seafloor. Here, we employ an integrated data‐model assessment that explicitly resolves benthic pH and carbonate chemistry along a South—North transect in the Barents Sea. We identify the main drivers of observed carbonate dynamics and estimate benthic fluxes of dissolved inorganic carbon and alkalinity to the Arctic Ocean. We explore how bottom water conditions and in‐situ organic matter degradation shape these processes and show that organic matter transformation strongly impacts pH and carbonate saturation (Ω) variations. Aerobic organic matter degradation drives a negative pH shift (pH < 7.6) in the upper 2–5 cm, producing Ω < 1. This causes shallow carbonate dissolution, buffering porewater pH to around 8.0. Organic matter degradation via metal oxide (Mn/Fe) reduction pathways further increases pH and carbonate saturation state. At the northern stations, where Ω > 5 at around 10–25 cm, model simulations result in authigenic carbonate precipitation. Furthermore, benthic fluxes of dissolved inorganic carbon (12.5–59.5 μmol cm−2 yr−1) and alkalinity (11.3–63.2 μmol cm−2 yr−1) are 2–3‐fold greater in the northern sites due to greater carbonate dissolution. Our assessment is of significant relevance to predict how changes in the Arctic Ocean may shift carbon burial and pH buffering into the next century.

Submarine metalliferous carbonate mounds in the Cambrian of the Baltoscandian Basin induced by vent networks and water column stratification

Two massive precipitation events of polymetallic ore deposits, encrusted by a mixture of authigenic carbonates, are documented from the Cambrian of the semi-enclosed Baltoscandian Basin. δ34S (‒9.33 to ‒2.08‰) and δ33S (‒4.75 to ‒1.06‰) values from the basal sulphide breccias, sourced from contemporaneous Pb–Zn–Fe-bearing vein stockworks, reflect sulphide derived from both microbial and abiotic sulphate reduction. Submarine metalliferous deposits were triggered by non-buoyant hydrothermal plumes: plumes of buoyant fluid were trapped by water column stratification because their buoyancy with respect to the environment reversed, fluids became heavier than their surroundings and gravitational forces brought them to a halt, spreading out laterally from originating vents and resulting in the lateral dispersion of effluents and sulphide particle settling. Subsequently, polymetallic exhalites were sealed by carbonate crusts displaying three generations of ikaite-to-aragonite palisade crystals, now recrystallized to calcite and subsidiary vaterite. Th of fluid inclusions in early calcite crystals, ranging from 65 to 78 ºC, provide minimum entrapment temperatures for carbonate precipitation and early recrystallization. δ13Ccarb (‒1.1 to + 1.6‰) and δ18Ocarb (‒7.6 to ‒6.5‰) values are higher than those preserved in contemporaneous glendonite concretions (‒8.5 to ‒4.7‰ and ‒12.4 to ‒9.1‰, respectively) embedded in kerogenous shales, the latter related to thermal degradation of organic matter. Hydrothermal discharges graded from highly reduced, acidic, metalliferous, and hot (~ 150 ºC) to slightly alkaline, calcium-rich and warm (< 100 ºC), controlling the precipitation of authigenic carbonates.

Seep dynamics as revealed by authigenic carbonates from the eastern Qiongdongnan Basin, South China Sea

Methane-related authigenic carbonates play a significant role in the marine carbon cycle and atmospheric CH4 budget. To elucidate the relationship between seeping methane and authigenic carbonate precipitation, we analyze a 72-cm long methane-related carbonate column from the W08 site in the Qiongdongnan Basin, South China Sea. Mineralogical composition, stable carbon and oxygen isotopes, major and trace element contents, and three-dimensional internal structure have been analyzed.Based on the results obtained, four types of carbonate are identified. The first type recorded decreasing content of rare earth elements plus yttrium (REEY) and increasing carbonate porosity. This is attributed to the gradual increase in methane flux intensity, raising the rate of carbonate deposition and thus reducing the time for elemental uptake. The second type of carbonate displays the same δ18O values as the theoretical equilibrium results, the maximum REEY contents, and the densely cemented carbonate structure, indicating a reduction in gas hydrate decomposition. The third type of carbonate formation occurring at the sediment-water interface shows a synchronous and significant enrichment of Mo, V, and Cd contents, suggesting the high hydrogen sulfide flux, which is subject to intensive methane flux and sulfate reduction. The fourth type is the late infill aragonite, which exhibits lower elemental contents compared to early cement due to less exposure to host sediments, while the difference in δ18O and δ13C values is not significant. The compilation of (Tb/Yb)N and Y/Ho ratios of cold-seep carbonates worldwide suggests that the methane flux could alter the space of redox zones (e.g. Fe reduction zone) and thus affect the sink of MREE.X-ray computed tomography (CT) reveals the internal structure of the methane-related carbonate. The continuous pore system probably suggests an intense fluid/gas pressure, and the in situ brecciations imply the carbonate precipitation did not entirely block the methane release to the water column. A better understanding of authigenic carbonates is fundamental to evaluating how carbonates modulate the carbon balance in the methane seeps.

Authigenic Clays Versus Carbonate Formation as Products of Marine Silicate Weathering in the Input Sequence to the Sumatra Subduction Zone

AbstractWe use geochemical and petrographic data from anoxic sequences of the Nicobar Fan to document extensive marine silicate weathering (MSiW) in the input sediment of the Sumatra subduction zone and the conditions that result in authigenic minerals originating from this reaction: precipitation of authigenic carbonate—which sequesters carbon—and formation of authigenic clay—which releases CO2. Increase in 87Sr/86Sr in pore fluids from International Ocean Discovery Program Expedition 362 (Site U1480 to 0.71376 and Site U1481 to 0.71296) reveals a radiogenic strontium contribution from alteration of the Himalayan continental sediment that dominates the Nicobar Fan. Peaks in the dissolved strontium isotope data coincide with zones of methane presence, consistent with MSiW reactions driven by CO2 generation during methanogenesis. Later‐stage fan sequences from 24 to 400 mbsf (meters below seafloor) contain only minor carbonate with 87Sr/86Sr ratios that deviate only slightly from the co‐eval seawater values (0.70920–0.70930); geochemical data in this zone point to a contribution of authigenic clay formation. In contrast, microscopy and elemental mapping of the carbonate‐cemented zones in the earliest fan deposits (&gt;780 mbsf) show replacement of feldspars and dense minerals by carbonate, which ranges in volume from a few percent of the grain to near total grain obliteration. This deeper authigenic carbonate is significantly enriched in radiogenic 87Sr (0.71136–0.71328). Thus, MSiW leads to distinct products, likely in response to a weathering‐derived supply of silica in the younger setting versus calcium enrichment via diffusion from oceanic basement in the older sequence.

Authigenic calcium carbonate precipitation in the “bathtub ring” around the anoxic Alum Shale Basin during the Furongian SPICE event (Baltic Basin, northern Poland)

ABSTRACT The precipitation of both biotic and abiotic calcium carbonate is of great importance in modern and ancient global biogeochemical cycles. In the present-day oceans, the widespread precipitation of inorganic CaCO3 on the seafloor or in the water column is possible only under extraordinary circumstances. By contrast, in the geological record, authigenic seafloor carbonate cements were widespread in the supersaturated, anoxic oceans of the Precambrian. Widespread authigenic carbonate precipitation ceased by the end of the Neoproterozoic as a consequence of global oceanic oxygenation: in the Phanerozoic, it occurred only during major anoxic events (for example, at the Permian/Triassic boundary) or in restricted, stagnant basins. Here, we present an anomalous record of CaCO3 precipitation from the Cambrian Alum Shale Basin of the Baltica palaeocontinent with Precambrian-like authigenic, seafloor encrusting, crystalline carbonates. The depositional environment of this well-recognized, cool-water, stagnant anoxic basin favoured local carbonate precipitation via the surplus generation of alkalinity in anoxic bottom waters. However, the correlation of the acme of authigenic carbonate formation with the onset and peak of the Steptoean Positive Carbon Isotope Excursion (SPICE) suggests a driver−trigger relation between the two phenomena. On a smaller scale, carbonate authigenic precipitation is manifested by a cement-supported texture of the limestone intercalations in the Alum Shale facies. Instantaneous calcification of the faunal remains, termed here the Snedronningen phenomenon, must have been of great importance in the formation of Orsten-type Konservat Lagerstätten.

Seasonal/Interannual Variation and Controlling Factors for Oxygen and Carbon Isotopes of Ostracod Shells Collected From a Time-Series Sediment Trap in Lake Qinghai

Because the shell substance of an ostracod is derived entirely from the water body where it lives, its chemical compositions are sensitive to aquatic environment and thus have been used to reconstruct past climatic and environmental changes. However, there is controversy about the controlling factors for the different compositions of ostracod shells from various water bodies. In this study, seasonal and interannual variations in daily flux and stable oxygen-carbon isotopic compositions (δ18O, δ13C) for two species of ostracod shells (Limnocythere inopinata and Eucypris mareotica) and their controlling factors are discussed, based on ostracod shell samples collected from a time-series sediment trap from July 2010 through September 2012 and from surface sediments in Lake Qinghai, which were correlated with the state-of-the-art sensing data of the lake water. The results show that the daily flux of L. inopinata shells is an order of magnitude higher than that of E. mareotica. The δ18O and δ13C of both L. inopinata and E. mareotica shells have distinctly interannual and seasonal variations, with species differences. Interannual differences of δ18O for the two species of ostracod shells directly reflect the systematic differences of the summer water temperature between 2010 and 2012. We propose that seasonal variations of both δ18O and δ13C for the two species are affected by the precipitation of authigenic carbonates in microenvironment induced by high water temperature in summers, highlighting their environmental implications in Lake Qinghai.

Methane-Derived Authigenic Carbonates on the Seafloor of the Laptev Sea Shelf

Seafloor authigenic carbonate crusts are widespread in various oceanic and marine settings, excluding high-latitude basins that are corrosive to carbonate precipitation. Newly formed carbonate formations are relatively rare in modern Arctic marine sediments. Although the first-order principles of seep carbonate formation are currently quite well constrained, little is known regarding the duration or mode of carbonate formation in the Siberian Arctic shelf. Large (massive slabs or blocks) and small crusts that were micrite cemented have been recently discovered on the seafloor of the Siberian Arctic seas within the area of known seep activity in the outer Laptev Sea shelf. Cold methane seeps were detected in the area due to the presence of an acoustic anomaly in the water column (gas flares). Microbial mats, methane gas bubbles, and carbonate crusts were observed using a towed camera platform. Here, we report new geochemical and mineralogical data on authigenic shallow Siberian Arctic cold-seep carbonate crusts to elucidate its genesis. The Laptev Sea carbonate crusts mainly consist of high-Mg calcite (up to 23 mol % MgCO3). The δ13C values in carbonates range significantly (from –40.1 to –25.9‰ VPDB), while the δ18O values vary in a narrow range (+4.4 ± 0.2‰ VPDB). The δ13C values of Corg that was determined from carbonates range from –40.2 to –31.1‰ VPDB. Using the isotope data and taking into account the geological setting, we consider that not only microbial but possibly thermogenic methane participated in the authigenic carbonate precipitation. Carbonate crust formation occurred below the water/sediment interface of the shallow Siberian Arctic shelf as a result of gas hydrate dissociation during Holocene warming events. The studied carbonate crusts were exhumated after precipitation into shallow subsurface shelf sediments.

Clay minerals modulate early carbonate diagenesis

Abstract Early diagenetic precipitation of authigenic carbonate has been a globally significant carbon sink throughout Earth history. In particular, SO42− and Fe3+ reduction and CH4 production create conditions in pore fluids that promote carbonate mineral precipitation; however, these conditions may be modified by the presence of acid-base buffers such as clay minerals. We integrated the acid-base properties of clay minerals into a biogeochemical model that predicts the evolution of pore-water pH and carbonate mineral saturation during O2, Fe3+, and SO42− reduction and CH4 production. Key model inputs were obtained using two natural clay mineral–rich sediments from the Integrated Ocean Drilling Program as well as from literature. We found that clay minerals can enhance carbonate mineral saturation during O2 and SO42− reduction and moderate saturation during Fe3+ reduction and CH4 production if the pore-fluid pH and clay mineral pKa values are within ~2 log units of one another. We therefore suggest that clay minerals could significantly modify the environmental conditions and settings in which early diagenetic carbonate precipitation occurs. In Phanerozoic marine sediments—where O2 and SO42− have been the main oxidants of marine sedimentary organic carbon—clay minerals have likely inhibited carbonate dissolution and promoted precipitation of authigenic carbonate.