Si Cycle Research Articles

Biogenic silica dynamics in coastal wetland sediments: A key driver of silicon and carbon biogeochemical cycling

AbstractBiogenic silica (biogenic Si) is a bioactive component crucial for the biogeochemical cycling of Si in terrestrial and aquatic ecosystems. Its formation and dissolution dynamics are intricately linked to carbon (C) cycling. However, knowledge about the source, composition, and factors controlling the distribution of biogenic Si in coastal wetland sedimentary environments is still limited. To address this lack of knowledge, we introduced a suite of geometric models for biogenic Si biovolume calculation and investigated biogenic Si assemblages, along with biogenic Si and biogenic Si‐occluded C contents, in sediments from representative coastal wetlands along the west coast of Bohai Bay. Our analysis showed that sedimentary biogenic Si predominantly derived from phytoliths (78.1% ± 5.8%), diatoms (18.2% ± 4.8%), and sponge spicules (3.7% ± 2.9%). Notably, phytolith assemblages were primarily composed of forms derived from the Poaceae family. The biogenic Si‐occluded C content (0.035–1.870 g kg−1) within these wetland sediments was consistent across both sites, accounting for 0.97–5.71% of the total organic C pool. Structural equation modeling indicated that total organic C, pH, and amorphous aluminum oxides either directly or indirectly influenced the biogenic Si content in coastal wetlands sediments. These results demonstrate the critical role that biogenic Si plays in the Si biogeochemical cycle and provide valuable information that advances our understanding of the biogeochemical interactions between Si and C in coastal wetland ecosystems.

Silicon balance in an integrated multi-tropical aquaculture ecosystem, Sanggou Bay, China

Farmed aquaculture species play an important role in regulating nutrient cycles in farming systems. Compared with nitrogen and phosphorus, the role of farmed species in the silicon (Si) cycle remains poorly understood. To help reduce this uncertainty, we clarified the sources and sinks of silicate and quantified the Si pools in an aquaculture system in Sanggou Bay (SGB). The results showed that dissolved inorganic nutrient levels were significantly lower during the dry season than during the wet. Dissolved silicate (DSi) is a potential limiting factor for phytoplankton growth during spring, and phosphorus limitation occurs during summer. The budget results indicated that large amounts of nitrogen, phosphate (DIP), and DSi were buried in the sediment or transformed into other forms during both the wet and dry seasons. The nitrogen and DIP cycles were strongly influenced by bivalve excretion and farmed species harvesting; however, these processes had little impact on the Si cycle. Si availability depends on both external inputs and internal recycling. DSi was primarily supplied from the Yellow Sea, with a minor contribution from the river due to river discharge during spring. However, during summer, riverine inflow (accounting for 83% of the total influx) was the major DSi source followed by benthic flux (12%). Biogenic silica (BSi) burial efficiency in the sediment was estimated to be 78% during spring and 23% during summer. The BSi preservation efficiency in bivalves during spring was high (53%), leading to a higher Si retention than in river discharge. Bivalves biodeposition plays an important role in the Si burial process. We suggest that this high retention is essentially controlled by the biodeposition mechanism, which is directly controlled by the exotic suspension feeders. Bivalves have the potential to alter Si retention in the bay by producing large amounts of biodeposits and accelerating the silica cycle, which may lead to more carbon dioxide being absorbed by diatoms.

Unraveling Morphology and Chemistry Dynamics in Fluoroethylene Carbonate Generated Silicon Anode Solid Electrolyte Interphase across Delithiated and Lithiated States

The silicon (Si) solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ~350% volume expansion. Understanding the SEI dynamic morphology and chemistry evolution from delithiated to lithiated states is thereby paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the dynamics of the FEC-SEI may provide hints toward engineering the Si interface. Herein, complementary ATR-FTIR, AFM, tip IR, and XPS probing reveal the presence of an elastomeric polycarbonate-like matrix in the FEC-generated SEI which is absent from the FEC-free SEI. Adding FEC to the baseline 1 M LiPF6 in EC:EMC (1:1) electrolyte promotes formation of a thinner and more conformal SEI, and subdues morphology and chemistry changes between consecutive half-cycles. From AFM, morphological stabilization of the FEC-SEI occurs earlier. Furthermore, conventional SEI biproducts such as Li2CO3 and LiEDC appear in reduced quantities in the FEC-SEI implying a reduced quantity of Li-consuming species. The thin polymeric FEC-SEI enables deeper (de)lithiation of silicon. In conclusion, the enhanced mechanical compliance, chemical invariance, and reduced Li inventory consumption of the FEC-SEI are logically the key features underlying the Si cycling enhancement by FEC.

The rise of biogenic silicon cycling and microbial silicification promoted Mesoproterozoic chert deposition

The silicon (Si) cycle is intimately interlinked with other biogeochemical cycles (e.g., carbon and nitrogen) and plays an important role in regulating long-term global climate change and biotic evolution in Earth's history. The abundance of cherts in Mesoproterozoic shallow-marine carbonates implies unique environmental conditions for silica precipitation, but the driving mechanism behind the Si cycle in Mesoproterozoic oceans remains unclear. In this paper, we report an integrated study of the cherts from the ∼1.48 Ga Wumishan Formation of North China. The Wumishan cherts predominantly consist of microquartz (∼90%), with some silica-replaced carbonate (∼5%) and minor pyrite (∼1%) grains, indicating that the cherts were largely formed through primary silica precipitation. High germanium/silicon molar ratios (Ge/Si = 0.71–19.1 μmol/mol; mean = 8.83) and positive europium anomalies (Eu/Eu* = 0.41–2.42; mean = 1.41) of the cherts suggest a considerable contribution from hydrothermally derived Si. Diverse microbial components, including organic-rich filaments, EPS (extracellular polymeric substances) relics, mat fragments and picocyanobacteria fossils, are observed in the Wumishan cherts. These components, together with abundant organominerals resulted from the interactions of microbes and dSi in ambient environments, imply that microbial activities played critical roles in silica deposition. The Si liberated from degraded EPS or EPS-Si complex may have locally increased the dSi concentrations and changed chemical conditions in the substrate and pore-waters, promoting silica precipitation. Given that picocyanobacteria and some other prokaryotes can accumulate significant amounts of silica in their cells and EPS, biogenic silica from decomposed microbial biomass may have exerted an important influence on silica precipitation in shallow-marine environments of the Mesoproterozoic ocean.

Determination of silicon isotopic composition in soil using gas-source isotope ratio mass spectrometry by thermal decomposition of barium hexafluorosilicate

Determining the Si isotopic compositions of samples of the Earth’s surface is crucial to understanding the implications of the biogeochemistry cycling of Si. This study established an alternative method for high-precision Si isotopic measurement in soil samples using gas-source isotope ratio mass spectrometry, which involved the conversion of Si in the samples into SiF4 gas, which was purified cryogenically and collected for isotopic analysis. The proposed method was applied to determine the Si isotopic composition of two reference materials (GBW04421 and GBW04422), and the results were found to be in good agreement with the certified values. Moreover, the proposed method exhibited a long-term measurement precision of 0.05 ‰–0.08 ‰ (2 s) for the δ30Si values. The δ30Si values obtained from ten soil reference materials ranged from −1.84 ‰ to −0.17 ‰, which were within the range of the values reported in the literature (−1.82 ‰ to −0.15 ‰). The sample preparation and analysis method in this study provided an easy and effective approach to determining the Si isotopic composition of solid samples and offers to the promise of being applicable to biogeochemical analyses of the Earth’s surface processes.

Microwave plasma atomic emission spectroscopy (MP-AES)—A useful tool for the determination of silicon contents in plant samples?

The accurate quantification of silicon (Si) contents in plant materials represents a fundamental prerequisite for agricultural plant-soil system or terrestrial ecosystem studies. Si contents in plants are usually calculated from Si concentrations determined spectroscopically in corresponding plant extracts. Inductively coupled plasma optical emission spectrometry (ICP-OES) is widely used in environmental sciences for Si measurements, because this technique is characterized by relatively high sensitivity and low expenditure of human labor. However, as an ICP-OES instrument is also characterized by relatively high acquisition and running costs, it is not readily available to most laboratories. Microwave plasma atomic emission spectroscopy (MP-AES) might represent a cost-effective alternative to ICP-OES. In our study we compared the results obtained from ICP-OES and MP-AES measurements of Si concentrations in Tiron extracts of husk and straw samples of winter wheat (Triticum aestivum) to evaluate the capability of the MP-AES technique for the determination of Si contents in plant materials. Moreover, we correlated these results with data on plant available Si concentrations in corresponding soil samples as well as phytolith contents in the husk and straw samples to evaluate the performance of MP-AES in biogeochemical Si plant-soil studies. Based on our results we found MP-AES to represent a suitable technique for the reliable determination of Si concentrations in Tiron extracts with negligible matrix effects. Our results clearly indicate that MP-AES represents a promising alternative for all researchers with a focus on biogeochemical Si cycling in general.

Unraveling Morphology and Chemistry Dynamics in Fluoroethylene Carbonate Generated Silicon Anode Solid Electrolyte Interphase Across Delithiated and Lithiated States: Relative Cycling Stability Enabled by an Elastomeric Polymer Matrix

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ∼350% volume expansion. Understanding the SEI dynamic morphology and chemistry evolution from delithiated to lithiated states is thereby paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the dynamics of the FEC-SEI may provide hints toward engineering the Si interface. Herein, complementary ATR-FTIR, AFM, tip IR, and XPS probing reveal the presence of an elastomeric polycarbonate-like matrix in the FEC-generated SEI which is absent from the FEC-free SEI. Adding FEC to the baseline 1 M LiPF6 in EC:EMC (1:1) electrolyte promotes formation of a thinner and more conformal SEI, and subdues morphology and chemistry changes between consecutive half-cycles. From AFM, morphological stabilization of the FEC-SEI occurs earlier. Furthermore, conventional SEI biproducts such as Li2CO3 and LiEDC appear in reduced quantities in the FEC-SEI implying a reduced quantity of Li-consuming species. The thin polymeric FEC-SEI enables deeper (de)lithiation of silicon. In conclusion, the enhanced mechanical compliance, chemical invariance, and reduced Li inventory consumption of the FEC-SEI are logically the key features underlying the Si cycling enhancement by FEC.

Atypical Seasonality of the Silicon Cycle in the Yellow River Estuary and Bohai Sea Revealed by Stable Silicon Isotopes

AbstractBiogeochemical Si cycle in coastal areas is of vital importance due to its close link with the carbon cycle. However, the coastal Si cycle has been heavily perturbated by human activities. In this study, we studied the spatiotemporal distribution of biogenic Si (BSi) and dissolved Si (DSi) combined with stable Si isotopes of DSi (δ30SiDSi) in the Yellow River estuary and Bohai Sea, one of the most populated coastal areas in the world. Over an annual cycle, BSi and DSi concentrations varied from 0 to 43.5 μmol L−1 and from 0.3 to 40 μmol L−1, respectively. This was associated with large δ30SiDSi variations from +0.49 ± 0.22‰ (2sd) in spring to +2.92 ± 0.14‰ in winter, which opposed to observations that summer δ30SiDSi values were usually higher than those in winter. This atypical variation could be attributed to the water‐sediment regulation on the Yellow River occurring every early summer, leading to a strong water mixing pattern and suppressing diatom production in summer. This mixing was further prolonged by extreme autumn rainfall on land. The pulse supply of nutrients subsequently enhanced primary productivity from autumn through winter. In spring, the resuspended seafloor sediments were likely an important DSi source with δ30Si values of <−0.5‰. Our findings suggest that natural Si seasonality has been greatly masked by human activities and climate events in the Bohai Sea. Our study serves as a reference of the Si cycle research endeavors worldwide for revealing the overlaying effect of anthropogenic consequences and natural variability.

Far-field effects of the Nile damming on the silica cycle in the Southeastern Mediterranean Sea

Silica plays a key role in the growth of silicifying primary producers (e.g., diatoms) and hence the ocean carbon pump. The Mediterranean Sea's eastern Levantine Basin (ELB) is a low silica (and low N and P) ultra-oligotrophic basin. Before 1965, Nile autumn floods were a major source of dissolved silica (DSi) and other nutrients to primary producers of the ELB continental shelf, also known as the Nilotic cell. The construction of the Aswan High Dam (AHD) in the mid-1960s, blocked these floods, drastically diminishing the autumn-diatom blooms offshore the Nile delta. However, the far-reaching and long-lasting effects of the Nile damming on the Si cycle in the ELB remain unclear. Here, we studied the changes in DSi in the surface water offshore Israel and the distribution of biogenic silica in deep-sea short sediment cores, collected hundreds of kilometers from the Nile outlet, at depths range of 1100–1900 m, offshore the ELB Israeli coast. We show post dam reduction and termination in flood related seasonality of DSi and a concurrent decrease (of up to 79 %) in biogenic silica (BSi) accumulation rates in surficial sediments relative to underlying sediments. These changes reflect the effects of Si (dissolved and particulate) retention by the AHD on diatoms production, export and burial in the ELB. This far-field effect was demonstrated in deep-sea areas subjected to intense lateral transport of resuspended sediments from the shelf via intermediate nepheloid layers and to coastal water intrusions, along the path of the pre-dam, flood plumes. Our core records show that the AHD worsened nutrient-diminished, exceptionally unfavorable conditions for diatoms that persisted in the deep ELB at least during the last four millennia.

Establishing fluvial silicon regimes and their stability across the Northern Hemisphere

AbstractFluvial silicon (Si) plays a critical role in controlling primary production, water quality, and carbon sequestration through supporting freshwater and marine diatom communities. Geological, biogeochemical, and hydrological processes, as well as climate and land use, dictate the amount of Si exported by streams. Understanding Si regimes—the seasonal patterns of Si concentrations—can help identify processes driving Si export. We analyzed Si concentrations from over 200 stream sites across the Northern Hemisphere to establish distinct Si regimes and evaluated how often sites moved among regimes over their period of record. We observed five distinct regimes across diverse stream sites, with nearly 60% of sites exhibiting multiple regime types over time. Our results indicate greater spatial and interannual variability in Si seasonality than previously recognized and highlight the need to characterize the watershed and climate variables that affect Si cycling across diverse ecosystems.

Well-Dispersed Bi nanoparticles for promoting the lithium storage performance of Si Anode: Effect of the bridging Bi nanoparticles

Silicon (Si) is considered a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical specific capacity of up to 4200 mAh/g. However, the poor cycling and rate performances of Si induced by the low intrinsic electronic conductivity and large volume expansion during the lithiation/delithiation process limit its practical application. Herein, a novel silicon/bismuth@nitrogen-doped carbon (Si/Bi@NC) composite with nanovoids was synthesized and investigated as an advanced anode material for LIBs. In such a structure, ultrafine bismuth nanoparticles coupled with an N-doped carbon layer were introduced to modify the surface of Si nanoparticles. Subsequently, the lithiated LixBi has excellent high ionic conductivity and acts as a fast transport bridge for lithium ions. The introduced carbon coating layer and nanovoids can buffer the volume expansion of Si during the lithiation/delithiation process, thus maintaining structural stability during the cycling process. As a result, the Si/Bi@NC composite exhibits excellent electrochemical performance, providing a relatively high capacity of 955.8 mAh/g at 0.5 A/g after 450 cycles and excellent rate performance with a high capacity of 477.8 mAh/g even at 10.0 A/g. Furthermore, the assembled full cell with LiFePO4 as cathode and pre-lithium Si/Bi@NC as anode can provide a high capacity of 138.8 mAh/g at 1C after 90 cycles, exhibiting outstanding cycling performance.

Muddy sediments are an important potential source of silicon in coastal and continental margin zones

The dissolution of silicate minerals on the seafloor releases an important amount of dissolved silicon (dSi), which is necessary for maintaining high diatom production in Coastal and Continental Margin Zones (CCMZs). However, the dissolution of silicate minerals along the continental shelves is variable, which hinders our understanding of the marine Si cycle on both a regional and global scale. To understand the discrepancy of silicon (Si) released in different sediment matrices and its potential controlling factors, we investigated surface sediments of typical CCMZs of the Chinese marginal Seas using a continuous alkaline extraction technique, grain size and chemical (carbon and total nitrogen) analysis as well as a qualitative measurement of clay mineral composition by X-ray diffraction. The results showed that the amount of Si and aluminum (Al) leached from muddy sediments were 2 times greater than those released from sandy sediments. High dissolution rates (> 0.20 mg-SiO2 g−1 min−1) of silicate minerals are caused by a large sediment-specific surface area. Further, our data showed that biogenic silica (bSi) with high Al content (Si:Al < 40) has low reactivity and that the source of Al incorporated in bSi is silicate minerals undergoing dissolution. We show that although the dissolution of silicate minerals is less active than that of bSi, it still potentially releases more bio-available Si and Al to seawater due to its dominant presence on the seafloor (70.3% − 99.0%wt). This study highlights silicate minerals as an important potential marine Si source and emphasizes the need for a better understanding of the roles of silicate minerals in the Si cycle of marginal seas in future studies.

The Role of Coastal Yedoma Deposits and Continental Shelf Sediments in the Arctic Ocean Silicon Cycle

AbstractThe availability of silicon (Si) in the ocean plays an important role in regulating biogeochemical and ecological processes. The Si budget of the Arctic Ocean appears balanced, with inputs equivalent to outputs, though it is unclear how a changing climate might aggravate this balance. In this study, we focus on Si cycling in Arctic coastal areas and continental shelf sediments to better constrain the Arctic Ocean Si budget. We provide the first estimate of amorphous Si (ASi) loading from erosion of coastal Yedoma deposits (30–90 Gmol yr−1), demonstrating comparable rates to particulate Si loading from rivers (10–90 Gmol yr−1). We found a positive relationship between surface sediment ASi and organic matter content on continental shelves. Combining these values with published Arctic shelf sediment properties and burial rates we estimate 70 Gmol Si yr−1 is buried on Arctic continental shelves, equivalent to 4.5% of all Si inputs to the Arctic Ocean. Sediment dissolved Si fluxes increased with distance from river mouths along cruise transects of shelf regions influenced by major rivers in the Laptev and East Siberian seas. On an annual basis, we estimate that Arctic shelf sediments recycle approximately up to twice as much DSi (680 Gmol Si) as is loaded from rivers (340–500 Gmol Si).

Testate amoebae (Protozoa) in lakes of the Qinghai-Tibet Plateau: Biodiversity, community structures, and protozoic biosilicification in relation to environmental properties and climate warming

The Qinghai-Tibet Plateau (QTP) is characterized by a vast number of frozen and unfrozen freshwater reservoirs, which is why it is also called “the third pole” of the Earth or “Asian Water Tower”. We analyzed testate amoeba (TA) biodiversity and corresponding protozoic biosilicification in lake sediments of the QTP in relation to environmental properties (freshwater conditions, elevation, and climate). As TA are known as excellent bio-indicators, our results allowed us to derive conclusions about the influence of climate warming on TA communities and microbial biogeochemical silicon (Si) cycling. We found a total of 113 TA taxa including some rare and one unknown species in the analyzed lake sediments of the QTP highlighting the potential of this remote region for TA biodiversity. >1/3 of the identified TA taxa were relatively small (<30 μm) reflecting the relatively harsh environmental conditions in the examined lakes. TA communities were strongly affected by physico-chemical properties of the lakes, especially water temperature and pH, but also elevation and climate conditions (temperature, precipitation). Our study reveals climate-related changes in TA biodiversity with consequences for protozoic biosilicification. As the warming trend in the QTP is two to three times faster compared to the global average, our results provide not only deeper insights into the relations between TA biodiversity and environmental properties, but also predictions of future developments in other regions of the world. Moreover, our results provide fundamental data for paleolimnological reconstructions. Thus, examining the QTP is helpful to understand microbial biogeochemical Si cycling in the past, present, and future.

Fabrication of Si Anode for Enhancing Electrochemical Performance by Electrodeposition Method

Silicon (Si) is one of the most abundant elements in the earth's crust and is important for the development of semiconductors, solar cells, and lithium ion battery (LIB)electrodes. silicon nanomaterials-based device production is currently hampered by high prices, high material consumption, and very sophisticated procedures of film deposition, including chemical vapour deposition (CVD) and plasma-enhanced chemical vapour deposition (PE-CVD).Future demand will need the development of cost-effective, simple, and high-throughput deposition techniques.moreover A large-scale use of Si anodes in LIB is hindered primarily by two factors: (a) a significant volume change (about 300%) during discharging and (b) the deterioration of silicon after several charging and discharging cycles. By covering silicon nanostructures with carbon nanomaterials that also improve the electrochemical performance of LIBs, these disadvantages may be eliminated. In order to meet all of these requirements, the electrodeposition approach may provide the means to create Si thin films in an aesthetic way. We studied We used water-contaminated BMImTf2N to electrolyze SiNPs on Graphene (Grn) -coated copper substrates at room temperature.SiNPs average 70-90 nanometres (nm). Grn layer on the Cu substrate enhances Si nucleation and prevents oxidation. At 0.5C, the charge capacity was 1350 mAh g-1 and the discharge capacity was 1588 mAh g-1. The columbic process's efficiency increased from 85% to 97% after 100 cycles. Grn's conductivity and volume expansion will boost Si's cycle life. Figure 1

(Invited) Extending Cycle and Calendar Life of Si Based Li-Ion Batteries By Localized High Concentration Electrolytes

Si is one of the most promising anode materials for the next generation of lithium (Li) ion batteries (LIBs). Recently, we have developed a porous Si with a unique carbon coating structure (“carbon on Si” instead of “Si on carbon”). The nano-porosity of the materials absorbed most of volume expansion so the particles (between 3-5 mm) can retain their integrity during cycling instead of breakdown observed in bulk Si particles. Although single layer pouch cells (Si/NMC622, 62 mAh) with this porous Si anode and baseline electrolyte (1.2 M LiPF6 in EC-EMC (3:7 by wt.) +10 wt.% FEC) can retain 91% capacity after 800 cycles, their calendar life is still far shorter from 10-year target required by electrical vehicles.In this work, we present a systematic investigation of the application of localized high concentration electrolyte (LHCE) to extend the cycle life and calendar life of Si-LIBs. A typical LHCE contains a Li salt (typically LiFSI) with high solubility in a common solvent (such as DMC), and a diluent (such as TTE) with minimal solubility of the Li salt. Compared with other electrolyte design, one distinct advantage of LHCE is that solvent and diluent in LHCE can be largely decoupled from each other: change in once components will have not significantly affect the functionality of other components. This characteristic of LHCE enables much more freedom in the electrolyte designs to satisfy different practical application needs (such as long cycle life, long calendar life, high rate, high temperature, and high voltage). For example, Si/NMC622 cells with a composition of LiFSI-2.15DMC-0.17VC-0.69FEC-4.31TTE (in molar ratio) have increased cycle life of Si/NMC622 pouch cells to 2000 cycles with 80% capacity retention at 25°C as compared with 1000 cycles when baseline electrolyte was used. However, this electrolyte is less stable when LiCoO2 is used as the cathode, leading to rapid capacity loss at elevated temperatures (45°C). One possible reason for this is that cobalt in the cathode leads to more rapid decomposition of FEC than in the case of NMC622 at 45°C. On the other hand, the stability of LHCE is significantly affected by the amount of free (unbound) solvent (including DMC, VC, and FEC in the above example) in the electrolyte. By minimizing the amount of total free solvents, an electrolyte with a composition of LiFSI-2DMC-0.1EC-0.1FEC-3TTE has led to a long cycle life of Si/NMC622 cells at 25°C. Increasing the amount of main solvent in the electrolyte can further increase the conductivity of the electrolyte and significantly increase the charge/discharge rate of the cells.The long calendar life of Si-LIBs can be measured by accelerated tests at elevated temperatures (up to 55°C). Although FEC-containing electrolytes can increase the cycle life of Si-LIBs at room temperature, most Si-LIBs with FEC-containing electrolytes exhibit a rapid increase in impedance at elevated temperature, leading to a short projected-calendar-life. We designed a series of experiments to investigate the effect of FEC on the calendar life of Si-LIBs. The results clearly indicate that the formation of a high impedance interphase layer on the anode and cathode surfaces due to the decomposition of FEC at high temperatures is one of the fundamental reasons for the short calendar life of Si-LIBs. By replacing FEC with an alternative additive, a new LHCE electrolyte has been designed that led to much better cycling stability of Si-LIBs at 45°C (less than 5% capacity loss in 500 cycles) and much longer calendar life. More details of these investigations will be reported in this presentation.

(Digital Presentation) Unraveling of the Morphology and Chemistry Dynamics in the FEC-Generated Silicon Anode SEI across Delithiated and Lithiated States

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ~350% volume expansion of Si which leads to shortened cell life during electrochemical cycling. Understanding the SEI morphology/chemistry and more importantly its dynamic evolution from delithiated and lithiated states is paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the effects of FEC on the dynamics of the resulting SEI may provide hints toward engineering the Si interface. Herein, ATR-FTIR, AFM, tip IR, and XPS probing all show pronounced relative invariance of the FEC-generated SEI compared to the FEC-free SEI between adjacent lithiated and delithiated states beyond the formation cycles. The SEI of Si thin film model surfaces in the baseline 1 M LiPF6 in EC:EMC (1:1) undergoes major morphological and chemical speciation swings between half-cycles while comparatively the SEI upon addition of FEC displays far less dynamic evolution. This morphology and chemistry stability of the FEC-SEI supports the enhanced cycling stability of silicon anodes in FEC-containing electrolytes. The experimental evidence gathered suggests that the FEC-SEI invariance is enabled by an elastomeric polycarbonate matrix that preserves the SEI integrity against the expansion of silicon upon lithiation. In turn, less electrolyte-consuming reconstruction occurs which manifests as and high LiF content from one half-cycle to the next. This work provides critical insights to enhance the silicon anode stability via targeted SEI engineering, namely that LiF protected by an elastomeric protective matrix may be key to buffering the unavoidable mechanical disruption. Figure 1

Silicon fractionations in coastal wetland sediments: Implications for biogeochemical silicon cycling

Coastal wetland sediment is important reservoir for silicon (Si), and plays an essential role in controlling its biogeochemical cycling. However, little is known about Si fractionations and the associated factors driving their transformations in coastal wetland sediments. In this study, we applied an optimized sequential Si extraction method to separate six sub-fractions of non-crystalline Si (Sinoncry) in sediments from two coastal wetlands, including Si in dissolved silicate (Sidis), Si in the adsorbed silicate (Siad), Si bound to organic matter (Siorg), Si occluded in pedogenic oxides and hydroxides (Siocc), Si in biogenic amorphous silica (Siba), and Si in pedogenic amorphous silica (Sipa). The results showed that the highest proportion of Si in the Sinoncry fraction was Siba (up to 6.6 % of total Si (Sitot)), followed by the Sipa (up to 1.8 % of Sitot). The smallest proportion of Si was found in the Sidis and Siad fractions with the sum of both being <0.1 % of the Sitot. We found a lower Siocc content (188 ± 96.1 mg kg−1) when compared to terrestrial soils. The Sidis was at the center of the inter-transformation among Si fractions, regulating the biogeochemical Si cycling of coastal wetland sediments. Redundancy analysis (RDA) combined with Pearson's correlations further showed that the basic biogenic elements (total organic carbon and total nitrogen), pH, and sediment salinity collectively controlled the Si fractionations in coastal wetland sediments. Our research optimizes sediment Si fractionation procedure and provides insights into the role of sedimentary Si fractions in controlling Si dynamics and knowledge for unraveling the biogeochemical Si cycling in coastal ecosystems.

The Holocene silicon biogeochemistry of Yellowstone Lake, USA

Silicon (Si) is an essential macronutrient for diatoms, an important component of lacustrine primary productivity that represents a link between the carbon and silicon cycles. Reconstructions of lake silicon cycling thus provide an underexploited window onto lake and catchment biogeochemistry. Silicon isotope geochemistry has potential to provide these reconstructions, given the competing source and process controls can be deconvolved. The silica-rich volcanic and hydrothermal systems in Yellowstone National Park are a great source of dissolved silicon into Yellowstone Lake, a system with high silicon, and thus carbon, export rates and the formation of diatom–rich sediment. Yellowstone Lake sediments should be an archive of past silicon biogeochemistry, although the effect of sublacustrine hydrothermal activity or hydrothermal explosion events is unclear.Here, we analysed lake water, tributaries, and hydrothermal vent fluids from Yellowstone Lake for their dissolved Si concentrations, isotope composition (δ30Si) and Ge/Si ratios to evaluate the sources of variability in the lake's Si cycle. Bulk elemental composition and biogenic SiO2 (bSiO2) content, together with δ30Si and Ge/Si ratios from a single diatom species, Stephanodiscus yellowstonensis, were analysed in two sediment cores spanning the last 9880 cal. yr BP. We investigate these datasets to identify long term Holocene changes in hydrothermal activity and effects of large and short-term events i.e., hydrothermal and a volcanic eruption.Combinations of bSiO2, δ30Si and Ge/Si with XRF and lithology data revealed that Yellowstone Lake has a resilient biogeochemical system: hydrothermal explosions are visible in the lithology but have no identifiable impact on bSiO2 accumulation or on the δ30Si signature. Both cores show similarities that suggest a stable and homogeneous dSi source across the entire lake. A narrow range of δ30Si and Ge/Si values suggests that the productive layer of the lake was well mixed and biogeochemically stable, with consistently high hydrothermal inputs of Si throughout the Holocene to buffer against the disturbance events. Variation in bSiO2 concentration through time is weakly correlated with an increase towards younger sediment in the δ30Si fossil diatom record in both cores. This increase mirrors that seen in ocean records, and follows changes known in summer insolation, summer temperatures and lake water-column mixing since the deglaciation. This suggests that climate forcing, and soil formation ultimately govern the silicon isotope record, which we suggest is via a combination of changes in weathering stoichiometry, diatom production, and relative proportion of dSi sources.

The accumulation and carbon sequestration potential of biogenic silica in coastal salt marshes: Implications for relative sea-level rise

The fate of soil biogenic silica (BSi) in coastal salt marshes is of global importance because of its role in providing both available silicon (Si) for the growth of plants and diatoms and in sequestering carbon (C) (blue C) in soils and sediments. However, the accumulation of BSi and BSi-occluded C (BSiOC) under different vegetation habitats in coastal ecosystems, particularly in response to relative sea‐level rise (RSLR), remains poorly understood. Here we established a paired waterlogging-control system and collected the soil samples under both waterlogged and non-waterlogged conditions from three vegetation habitats (single Phragmites australis, a mixture of P. australis and Suaeda salsa, and single S. salsa) corresponding to a gradient of distance from the coastline in three independent salt marshes. Our findings indicated that RSLR decreased average BSi content, especially in the 0–20 cm soil layer of the single P. australis and the mixed P. australis and S. salsa community. Although RSLR increased soil organic C (SOC) content, it generally decreased soil BSiOC content and its contribution to SOC. Consequently, RSLR resulted in lower soil BSi and BSiOC densities, particularly in the salt marsh dominated by the Si accumulator P. australis. Here, BSi and BSiOC densities at depths of 0–80 cm decreased by an average of 19% and 18% following waterlogging, respectively. The BSi pool was dominated by phytoliths in non-waterlogged soils, while both diatoms and phytoliths were present in soils subjected to RSLR. Soil physicochemical properties including SOC, electrical conductivity and dissolved Si were influenced by RSLR. These factors, along with erosion were suggested as key influencers for BSi and its C sequestration in coastal salt marshes. Our results provide a scientific basis for elucidating biogeochemical Si cycles and predicting changes in BSiOC sequestration to optimize its storage.