Alteration of silicate phases in marine sediments is important for the global budget of carbon, silicon, and many other elements. Despite the growing recognition of in-situ marine silicate alteration (dissolution and formation), its global significance and controlling factors are still poorly understood. By compiling data from scientific drilling and applying numerical modelling, we investigate the interactions between two connected feedback loops: the particulate organic-inorganic carbon loop and the forward-reverse silicate weathering loop. By simulating early diagenetic sequences in the top tens of meters of sediments, we examined the saturation state and interactions of a wide range of silicate minerals. When organic matter is degraded at moderate rates, iron- and sulfate-reduction elevate porewater pH and create a condition that favours reverse weathering driven by the formation of smectite-group clay phases. Our simulations estimate an up to 10 % increase in DIC flux towards the oxic surface sediments with no substantial change in the alkalinity flux. On the other hand, fast organic matter degradation acidifies pore fluids in extended methanogenic zones and induces dissolution of silicates. Dissolution of several reactive silicate phases (mica, amphibole, and pyroxene groups) buffers porewater pH by effectively converting dissolved CO₂ to carbonate alkalinity and results in marine silicate weathering. Consequently, the total alkalinity flux towards oxic sediments increases by as much as 11 % under this condition. The analyses of a global database of pore fluid composition suggest dominant weathering of K- and Mg-containing silicate minerals that can be identified visually. Higher-than-seawater Mg concentrations were observed in almost all sites where total alkalinity is >56 meq/L, with Mg accounting for up to 40 % of the measured alkalinity. Modelling of this data compilation points to dissolution of Mg- and K-rich mica-group silicates as the primary cause for the elevated total alkalinity. The degree of TA excess seems to increase at sites with greater burial thermal history below the sulfate reduction zone with two trends observed among different continental margins. Such a relationship is however not always statistically significant due to the limited number of study sites in certain margins.

Organic matter degradation determines the overall level and flux of DIC as well as dissolved CO₂ in pore fluids, with DIC speciation is modulated through silicate alteration and carbonate authigenesis. As demonstrated by our numerical modelling, increasing organic matter degradation rate four-fold leads to 6.1 times higher fluxes of DIC and total alkalinity towards the oxic sediments, with marine silicate alteration contributing ca. 10-11 % of the changes in DIC fluxes (for reverse weathering) and total alkalinity fluxes (for silicate weathering). We further show that the amounts of DIC sequestered as authigenic carbonate in the methanogenic sediments due to marine silicate weathering could be substantially lower than previous estimates but depends highly on the type of reactive silicate phases weathered. As expected, reverse weathering increases fluxes of dissolved CO₂. However, an even greater increase in dissolved CO₂ flux is predicted when organic matter is rapidly degraded, despite the pH buffering from active marine silicate weathering. The CSi coupling has the potential to modify fluxes of DIC, total alkalinity, and likely other major dissolved constituents between marine sediments and the overlying bottom seawater. However, interpreting the convoluted feedback between organic matter degradation, marine silicate alteration, and carbonate authigenesis requires integrated efforts that take field observations, theoretical consideration, and laboratory constraints into consideration.

Coastal areas are an important source of methane (CH4). However, the exact origins of CH4 in the surface waters of coastal regions, which in turn drive sea-air emissions, remain uncertain. To gain a comprehensive understanding of the current and future climate change feedbacks, it is crucial to identify these CH4 sources and processes that regulate its formation and oxidation. This study investigated coastal CH4 dynamics by comparing water column data from six stations located in the brackish Tvärminne Archipelago, Baltic Sea. The sediment biogeochemistry and microbiology were further investigated at two stations (i.e., nearshore and offshore). These stations differed in terms of stratification, bottom water redox conditions, and organic matter loading. At the nearshore station, CH4 diffusion from the sediment into the water column was negligible, because nearly all CH4 was oxidized within the upper sediment column before reaching the sediment surface. On the other hand, at the offshore station, there was significant benthic diffusion of CH4, albeit the majority underwent oxidation before reaching the sediment-water interface, due to shoaling of the sulfate methane transition zone (SMTZ). The potential contribution of CH4 production in the water column was evaluated and was found to be negligible. After examining the isotopic signatures of δ13C-CH4 across the sediment and water column, it became apparent that the surface water δ13C-CH4 values observed in areas with thermal stratification could not be explained by diffusion, advective fluxes, nor production in the water column. In fact, these values bore a remarkable resemblance to those detected below the SMTZ. This supports the hypothesis that the source of CH4 in surface waters is more likely to originate from ebullition than diffusion in stratified brackish coastal systems.

Sea-ice dynamics can affect carbon cycling in polar oceans, with sea-ice ikaite acting as a potentially important carbon pump. However, there is no large-scale direct field evidence to support this. Here we used a unique data set that combined continuous measurements of atmospheric and water CO2 concentrations with water chemistry data collected over 1,200 km along the East Siberian Sea, the widest Arctic shelf sea. Our results reveal large spatial heterogeneity of sea-ice ikaite contents, which directly interact with carbonate chemistry in the water column. Our findings demonstrate that the CO2 drawdown by sea-ice ikaite dissolution could be as important as that by primary production. We suggest that the role of ikaite in regulating the seasonal carbon cycle on a regional scale could be more important than we previously thought. Effects of the warmer climate on sea ice loss might also play a role in the ikaite inventory.

Coastal ecosystems can efficiently remove carbon dioxide (CO₂) from the atmosphere and are thus promoted for nature-based climate change mitigation. Natural methane (CH₄) emissions from these ecosystems may counterbalance atmospheric CO₂ uptake. Still, knowledge of mechanisms sustaining such CH₄ emissions and their contribution to net radiative forcing remains scarce for globally prevalent macroalgae, mixed vegetation, and surrounding depositional sediment habitats. Here we show that these habitats emit CH₄ in the range of 0.1 – 2.9 mg CH₄ m⁻² d⁻¹ to the atmosphere, revealing in situ CH₄ emissions from macroalgae that were sustained by divergent methanogenic archaea in anoxic microsites. Over an annual cycle, CO₂-equivalent CH₄ emissions offset 28 and 35% of the carbon sink capacity attributed to atmospheric CO₂ uptake in the macroalgae and mixed vegetation habitats, respectively, and augment net CO₂ release of unvegetated sediments by 57%. Accounting for CH₄ alongside CO₂ sea-air fluxes and identifying the mechanisms controlling these emissions is crucial to constrain the potential of coastal ecosystems as net atmospheric carbon sinks and develop informed climate mitigation strategies.

Silicon (Si) phases such as biogenic silica, lithogenic silicate and authigenic silica/silicate in marine sediments provide valuable information about past Si cycling. Wet-chemical sequential leaching methods are often applied to extract different Si phases from marine sediments to study Si diagenetic processes in shallow subsurface. The potential of this method to separate Si phases from deeply-buried and diagenetically-modified sediments has not been systematically examined. We applied a sequential leaching protocol to drill core sediments retrieved from the Ulleung Basin, East/Japan Sea. We performed geochemical (elemental abundance and stable Si isotopes, δ³⁰Si) and microscopic (X-ray diffraction and scanning electron microscope) analyses to monitor leaching efficiency in separating different Si phases. We show that, prior to alkaline leaching, applying weak acid is able to remove metal oxide and/or clay-like phases. The following Na₂CO₃ leaching, based on a commonly-adopted protocol, is able to dissolve some but not all diatoms. The results of elemental contents and δ³⁰Si values of leachates suggest that, in diagenetically-modified sediments, either a longer digesting time or a harsher alkaline leaching is needed to dissolve all diatoms. This is attributed to increased resistance of diatoms to Na₂CO₃ leaching as a result of reduced surface area and/or improved SiO₂ tetrahedron ordering during diagenetic processes over time and burial depths. Lithogenic silicate minerals can be dissolved by NaOH and potentially separated from diatoms if the latter is completely removed in the preceding leaching steps. Even if a trace amount of diatom is left undissolved in the NaOH leaching, it is still possible to separate the two through a mass balance calculation given the knowledge of composition for the two end-members. We conclude that a successful separation of Si phases in diagenetically modified sediments relies on the knowledge of elemental abundance and even δ³⁰Si values of the leachates, as well as information such as species of Si-skeleton organisms, contents and maturation degree of biogenic silica.

Phytolith carbon (C) sequestration plays a key role in mitigating global climate change at a centennial to millennial time scale. However, previous estimates of phytolith-occluded carbon (PhytOC) storage and potential in China's grasslands have large uncertainties mainly due to multiple data sources. This contributes to the uncertainty in predicting long-term C sequestration in terrestrial ecosystems using Earth System Models. In this study, we carried out an intensive field investigation (79 sites, 237 soil profiles [0–100 cm], and 61 vegetation assessments) to quantify PhytOC storage in China's grasslands and to better explore the biogeographical patterns and influencing factors. Generally, PhytOC production flux and soil PhytOC density in both the Tibetan Plateau and the Inner Mongolian Plateau had a decreasing trend from the Northeast to the Southwest. The aboveground PhytOC production rate in China's grassland was 0.48 × 10⁶ t CO₂ a^–1, and the soil PhytOC storage was 383 × 10⁶ t CO₂. About 45% of soil PhytOC was stored in the deep soil layers (50–100 cm), highlighting the importance of deep soil layers for C stock assessments. Importantly, the Tibetan Plateau had the greatest contribution (more than 70%) to the PhytOC storage in China's grasslands. The results of multiple regression analysis indicated that altitude and soil texture significantly influenced the spatial distribution of soil PhytOC, explaining 78.1% of the total variation. Soil phytolith turnover time in China's grasslands was mainly controlled by climatic conditions, with the turnover time on the Tibetan Plateau being significantly longer than that on the Inner Mongolian Plateau. Our results offer more accurate estimates of the potential for phytolith C sequestration from ecological restoration projects in degraded grassland ecosystems. These estimates are essential to parameterizing and validating global C models.

Coastal regions globally have experienced widespread anthropogenic eutrophication in recent decades. Loading of autochthonous carbon to coastal sediments enhances the demand for electron acceptors for microbial remineralization, often leading to rearrangement of the sediment diagenetic zonation and potentially enhancing fluxes of methane and hydrogen sulfide from the seafloor. However, the role of anthropogenic inputs of terrestrial organic matter (OM_terr.) in modulating diagenesis in coastal sediments is often overlooked, despite being of potential importance in regions of land-use and industrial change. Here we present a dated 4-m sediment and porewater geochemistry record from a eutrophic coastal location in the northern Baltic Sea, to investigate sources of recent carbon loading and their impact on modern diagenetic processes. Based on an end-member mixing model of sediment N/C ratios, we observe that a significant fraction of the late-20th century carbon loading at this location was contributed by OM_terr.. Furthermore, analysis of lignin in this material shows depleted ratios of syringyl/vanillyl (S/V) and cinnamyl/vanillyl (C/V) phenols, indicative of enhanced inputs of woody gymnosperm tissue likely from forest industries. The rapid loading of organic matter from combined terrestrial and autochthonous sources during the late 20th century has stimulated methanogenesis in the sediment column, and shoaled the sulfate-methane transition zone (SMTZ) to a depth of 5–20 cm. Optical parameters of colored dissolved organic matter confirm that OM_terr. is actively degrading in the methanogenic layer, implying a role for this material in diagenetic processes. Porewater CH₄, SO₄²⁻ δ¹³C-DIC, and ∑S²⁻ data suggest that the modern SMTZ is a broad zone in which organoclastic sulfate reduction, methanogenesis and anaerobic oxidation of methane (AOM) co-occur. However, fluxes of CH₄ and SO₄²⁻ show that rates of these processes are similar to other marine locations with a comparably shallow SMTZ. We suggest that the shallow depth of the modern SMTZ is the principal reason for high observed diffusive and ebullitive methane fluxes from sediments in this area. Our results highlight that anthropogenic activities lead to multiple pathways of carbon loading to coastal sediments, and that forest industry impacts on sedimentation in the northern Baltic Sea may be more widespread than previously acknowledged.

We present pore fluid geochemistry, including major ion and trace metal concentrations and the isotopic composition of pore fluid calcium and sulfate, from the uppermost meter of sediments from the Gulf of Aqaba (Northeast Red Sea) and the Iberian Margin (North Atlantic Ocean). In both the locations, we observe strong correlations among calcium, magnesium, strontium, and sulfate concentrations as well as the sulfur isotopic composition of sulfate and alkalinity, suggestive of active changes in the redox state and pH that should lead to carbonate mineral precipitation and dissolution. The calcium isotope composition of pore fluid calcium (delta Ca-44) is, however, relatively invariant in our measured profiles, suggesting that carbonate mineral precipitation is not occurring within the boundary layer at these sites. We explore several reasons why the pore fluid delta Ca-44 might not be changing in the studied profiles, despite changes in other major ions and their isotopic composition, including mixing between the surface and deep precipitation of carbonate minerals below the boundary layer, the possibility that active iron and manganese cycling inhibits carbonate mineral precipitation, and that mineral precipitation may be slow enough to preclude calcium isotope fractionation during carbonate mineral precipitation. Our results suggest that active carbonate dissolution and precipitation, particularly in the diffusive boundary layer, may elicit a more complex response in the pore fluid delta Ca-44 than previously thought.

The vast majority of carbonate minerals in modern marine sediments are biogenic, derived from the skeletal remains of organisms living in the ocean. However, carbonate minerals can also precipitate abiotically within marine sediments, and this carbonate mineral precipitation within sediments has been suggested as a third major, and isotopically distinct, sink in the global carbon cycle, particularly important earlier in Earth history. Here we present a global compilation of pore fluid data and compare the sulfate, calcium, phosphate and magnesium concentrations with pore fluid alkalinity to explore the emerging relationships and explore what drives carbonate mineral precipitation in sediments. Our data compilation shows that the gradient of pore fluid sulfate concentrations correlates strongly with the gradient of alkalinity as well as with the gradient of calcium, and that these correlations improve dramatically in sediments where methane is present. We also note that sedimentary pore fluids that are high in phosphate concentration are also high in alkalinity, which may indicate suppression of carbonate mineral precipitation in the presence of sedimentary phosphate. Our data can be used to highlight sediments where both dolomite formation and dolomitization of previously deposited calcium carbonate minerals is occurring. We explore how carbonate mineral saturation state changes as a function of calcium concentrations, alkalinity, and pH, and suggest a reason why calcium concentrations are never fully depleted in sedimentary pore fluids. We conclude that carbonate minerals precipitate in sediments with methane, where the anaerobic oxidation of this methane helps promote particularly high saturation states for carbonate minerals.

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ³⁴S and δ¹⁸O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ³⁴S and δ¹⁸O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ³⁴S and δ¹⁸O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.