Biogeochemical Cycle Of Silicon Research Articles

Controls on riverine δ30Si signatures in a temperate watershed under high anthropogenic pressure (Scheldt — Belgium)

We analysed Si isotopic signatures (δ30Si signature) of dissolved silicon (DSi) in the Scheldt (Belgium) tidal river (four stations) and in its main tributaries (Zenne, Dender, Grote Nete and Kleine Nete). For each station, we analysed four samples representative of the four seasons. These are the first δ30Si data at the basin and seasonal scales measured in a watershed under high anthropogenic pressure. In the Scheldt main stem, we show that the role of diatoms on the silicon biogeochemical cycle and δ30Si signatures is dominant in summer and sometimes in fall. Out of the diatoms' growing season, the Scheldt main stem exhibits unexpected large δ30Si signatures variations, especially in winter. Although these isotopic variations are not reflected in DSi concentrations, they are consistent with δ30Si signatures recorded in the main tributaries. This indicates that except for summer diatom blooms, δ30Si signatures in the tidal river result from a conservative mixing with tributaries. Overall we suggest that the variations are mainly set by land use and lithology at the sub-basin level. Forest cover (inducing clay dissolution favoured by the presence of humic acids) and wetland cover (yielding to dissolution of biogenic silica) are highly and significantly correlated with δ30Si (R2>0.85). Both environments tend to render the tributaries δ30Si signatures lighter while agriculture cover has the reverse effect on δ30Si values (R2=0.70, p-value<0.08). In contrast, urban zone cover does not have any noticeable effect on Si isotopic signatures of the Scheldt tributaries. Despite this effect of land use, we estimate a mean annual δ30Si signature output from the Scheldt tidal river to the saline estuary at 0.95‰, well comparable to other rivers. This results from the mixing of tributaries within the tidal river which levels off at the outlet the Si isotopic differences of the sub-basins. In the Scheldt watershed, it thus seems that Si isotopes could trace anthropogenic activities at the sub-basin scale. In contrast, at the outlet, the variety of land-use and lithology found over the whole watershed are merged into a mean isotopic signature similar to the world river average. As it is now recognised that change in land use alter the silicon biogeochemical continental cycle, our data show that use of Si isotopic signatures might constitute a useful proxy to better trace these modifications on contrasted (sub-)basins.

稻田生态系统中植硅体的产生与积累——以嘉兴稻田为例

Phytolith,the opal of amorphous silica formed in plant tissues( e. g.,cell walls,cell luminas,and intercellular spaces typically near evaporating surfaces),presents in most plants. This study selected plants of five rice cultivars of Jiahua11,Zhejing37, Ning81, Xianghu301, Xiushui09 and their corresponding surface soils( 0—10 cm) at the experiment base of Hangjiahu plain in Jiaxing,to investigate the fluxes of the phytolith production and accumulation in rice ecosystems. The main purpose of this study is to provide scientific reference for understanding the role of phytoliths in biogeochemical cycles of silicon and carbon. Results showed that the phytolith content varied from 40. 54 to 51. 40 g / kg, with an average of 46. 54 g / kg,being higher in Jiahua11,Ning81 and Xianghu 301 than that in Zhejing37 and Xiushui09 It decreased in the following order among different organs: sheath leaf stem root grains. There was a positive correlation between phytolith content and total SiO 2 in rice and soil,R2= 0. 8156( P0. 01) and R2= 0. 355( P0. 05), respectively. The total production flux of phytoliths for whole plants was 1269. 59 kg hm-2a-1. The aboveground and underground phytolith production flux was 1203. 44 and 66. 15 kg hm-2a-1,respectively. The flux of phytolith production differed in different rice cultivars. The flux of aboveground and underground phytolith production in Jiahua11 was higher than that of the other. The flux of phytolith production from root,stem,sheath,leaf and grains is 66. 15,131. 65, 491. 08,185. 36 and 395. 35 kg hm-2a-1,respectively. In rice ecosystems with 50 years of cultivation,the phytolith accumulation flux in surface soil( 0—10 cm) was 40. 38 kg hm-2a-1,which was equivalent to the flux of root phytolith production,implying that the rice straws are rarely returned to the paddy soil. The production flux of rice phytolith to sequestrate the atmospheric CO 2 was 46. 55—279. 31 kg hm-2a-1and the accumulation flux of paddy soil phytolith sequestrate the atmospheric CO 2 was 1. 48—8. 88 kg hm-2a-1. It was promising to improve the fluxes of phytolith production and the phytolith to sequestrate CO 2 by selecting high phytolith content rice varities such as Jiahua11.

A Review of the Biogeochemical Cycle of Silicon in Terrestrial Ecosystems

A Review of the Biogeochemical Cycle of Silicon in Terrestrial Ecosystems

Interactions of Amines with Silicon Species in Undersaturated Solutions Leads to Dissolution and/or Precipitation of Silica

The biogeochemical silicon cycle is the focus for many researchers studying the dissolution of silicon species from quartz, amorphous, and biogenic silica. Furthermore, the precipitation of biogenic silica by diatoms, radiolarian, sponges, and plants is also a popular focus for research. The ornate silica structures created by these species has attracted interest from biomaterial scientists and biochemists who have studied mineral formation in an attempt to understand how biogenic silica is formed, often in the presence of proteins and long chain polyamines. This article is at the interface of these seemingly distinct research areas. Here we investigate the effect of a range of amines in globally undersaturated silicon environments. Results are presented on the effect of amine-containing molecules on the formation of silica from undersaturated solutions of orthosilicic acid and globally undersaturated silicon environments. We sought to address two questions: can silica be precipitated/harvested from undersaturated solutions, and can we identify the silicon species that are most active in silica formation? We demonstrate that none of the bioinspired additives investigated here (e.g., poly(allylamine hydrochloride), pentaethylenehexamine, and propylamines) have any influence on orthosilicic acid at undersaturated concentrations. However, under globally undersaturated silicon concentrations, small molecules and polymers containing amine groups were able to interact with oligomers of silicic acid to either generate aggregated materials that can be isolated from solution or increase rates of oligomer dissolution back to orthosilicic acid. Additional outcomes of this study include an extended understanding of how polyelectrolytes and small molecules can promote and/or inhibit silica dissolution and a new method to explore how (bio)organic molecules interact with a forming mineral phase.

Human perturbations on the global biogeochemical cycles of coupled Si–C and responses of terrestrial processes and the coastal ocean

Abstract We present a model of the global biogeochemical cycle of silicon (Si) that emphasizes its linkages to the carbon cycle and temperature. The Si cycle is a crucial part of global nutrient biogeochemistry regulating long-term atmospheric CO2 concentrations due to silicate mineral weathering reactions involving the uptake of atmospheric CO2 and production of riverine dissolved silica, cations and bicarbonate. In addition and importantly, the Si cycle is strongly coupled to the other nutrient cycles of N, P, and Fe; hence siliceous organisms represent a significant fraction of global primary productivity and biomass. Human perturbations involving land-use changes, burning of fossil fuel, and inorganic N and P fertilization have greatly altered the terrestrial Si cycle, changing the river discharge of Si and consequently impacting marine primary productivity primarily in coastal ocean waters.

Deep silicon maxima in the stratified oligotrophic Mediterranean Sea

Abstract. The silicon biogeochemical cycle has been studied in the Mediterranean Sea during late summer/early autumn 1999 and summer 2008. The distribution of nutrients, particulate carbon and silicon, fucoxanthin (Fuco), and total chlorophyll-a (TChl-a) were investigated along an eastward gradient of oligotrophy during two cruises (PROSOPE and BOUM) encompassing the entire Mediterranean Sea during the stratified period. At both seasons, surface waters were depleted in nutrients and the nutriclines gradually deepened towards the East, the phosphacline being the deepest in the easternmost Levantine basin. Following the nutriclines, parallel deep maxima of biogenic silica (DSM), fucoxanthin (DFM) and TChl-a (DCM) were evidenced during both seasons with maximal concentrations of 0.45 μmol L−1 for BSi, 0.26 μg L−1 for Fuco, and 1.70 μg L−1 for TChl-a, all measured during summer. Contrary to the DCM which was a persistent feature in the Mediterranean Sea, the DSM and DFMs were observed in discrete areas of the Alboran Sea, the Algero-Provencal basin, the Ionian sea and the Levantine basin, indicating that diatoms were able to grow at depth and dominate the DCM under specific conditions. Diatom assemblages were dominated by Chaetoceros spp., Leptocylindrus spp., Pseudonitzschia spp. and the association between large centric diatoms (Hemiaulus hauckii and Rhizosolenia styliformis) and the cyanobacterium Richelia intracellularis was observed at nearly all sites. The diatom's ability to grow at depth is commonly observed in other oligotrophic regions and could play a major role in ecosystem productivity and carbon export to depth. Contrary to the common view that Si and siliceous phytoplankton are not major components of the Mediterranean biogeochemistry, we suggest here that diatoms, by persisting at depth during the stratified period, could contribute to a large part of the marine primary production as observed in other oligotrophic areas.

Tracing the origin of dissolved silicon transferred from various soil-plant systems towards rivers: a review

Abstract. Silicon (Si) released as H4SiO4 by weathering of Si-containing solid phases is partly recycled through vegetation before its land-to-rivers transfer. By accumulating in terrestrial plants to a similar extent as some major macronutrients (0.1–10% Si dry weight), Si becomes largely mobile in the soil-plant system. Litter-fall leads to a substantial reactive biogenic silica pool in soil, which contributes to the release of dissolved Si (DSi) in soil solution. Understanding the biogeochemical cycle of silicon in surface environments and the DSi export from soils into rivers is crucial given that the marine primary bio-productivity depends on the availability of H4SiO4 for phytoplankton that requires Si. Continental fluxes of DSi seem to be deeply influenced by climate (temperature and runoff) as well as soil-vegetation systems. Therefore, continental areas can be characterized by various abilities to transfer DSi from soil-plant systems towards rivers. Here we pay special attention to those processes taking place in soil-plant systems and controlling the Si transfer towards rivers. We aim at identifying relevant geochemical tracers of Si pathways within the soil-plant system to obtain a better understanding of the origin of DSi exported towards rivers. In this review, we compare different soil-plant systems (weathering-unlimited and weathering-limited environments) and the variations of the geochemical tracers (Ge/Si ratios and δ30Si) in DSi outputs. We recommend the use of biogeochemical tracers in combination with Si mass-balances and detailed physico-chemical characterization of soil-plant systems to allow better insight in the sources and fate of Si in these biogeochemical systems.

Fire and grazing impacts on silica production and storage in grass dominated ecosystems

Grassland ecosystems are an important terrestrial component of the global biogeochemical silicon cycle. Although the structure and ecological functioning of grasslands are strongly influenced by fire and grazing, the role of these key ecological drivers in the production and storage of silicon represents a significant knowledge gap, particularly since they are being altered worldwide by human activities. We evaluated the effects of fire and grazing on the range and variability of plant derived biogenic silica stored in plant biomass and soils by sampling plants and soils from long-term experimental plots with known fire and grazing histories. Overall, plants and soils from grazed sites in the South African ecosystems had up to 76 and 54% greater biogenic silica totals (kg ha−1), respectively, than grazed North American sites. In North American soils, the combination of grazing and annual fire resulted in the greatest abundance of biogenic silica, whereas South African soils had the highest biogenic silica content where grazed regardless of burn frequency. These results as well as those that show greater Si concentrations in grazed South African plants indicate that South African plants and soils responded somewhat differently to fire and grazing with respect to silicon cycling, which may be linked to differences in the evolutionary history and in the grazer diversity and grazing intensity of these ecosystems. We conclude that although fire and grazing (as interactive and/or independent factors) do not affect the concentration of Si taken up by plants, they do promote increased silicon storage in aboveground biomass and soil as a result of directly affecting other site factors such as aboveground net primary productivity. Therefore, as management practices, fire and grazing have important implications for assessing global change impacts on the terrestrial biogeochemical cycling of silicon.

When to say when: can excessive drinking explain silicon uptake in diatoms?

Diatoms are the single most important drivers of the oceanic silicon biogeochemical cycle. Due to their considerable promise in nanotechnology, there is tremendous interest in understanding the mechanism by which they produce their intricately and ornately decorated silica-based cell wall. Although specific proteins have been implicated in some of the key steps of silicification, the exact mechanisms are poorly understood.Silicon transporters, identified in both diatoms and silicoflagellates, are hypothesized to mediate silicon uptake. Recently, macropinocytosis, the non-specific engulfment of extracellular fluid, was proposed as a more energetically favorable uptake mechanism, which can also explain the long-observed effect of salinity on frustule morphology. We explore the bioenergetic, membrane recycling, and vacuolar volume requirements that must be satisfied for pinocytosis-mediated silicon uptake. These calculated requirements contrast starkly with existing data on diatom physiology, uptake kinetics, growth, and ultrastructure, leading us to conclude that pinocytosis cannot be the primary mechanism of silicon uptake.

Towards an understanding of late Quaternary variations in the continental biogeochemical cycle of silicon: multi‐isotope and sediment‐flux data for Lake Rutundu, Mt Kenya, East Africa, since 38 ka BP

AbstractSilicon is an essential nutrient for marine diatoms, which dominate the export of organic carbon to the deep ocean. Despite the dominance of the oceanic Si budget by fluvial inputs and the role of the land biosphere in controlling Si losses from rocks and soils to rivers, few studies have considered how continental biogeochemical Si fluxes varied on an orbital timescale. We reconstruct changes in Si cycling by the catchment‐lake ecosystem of Lake Rutundu, Mt Kenya (3078 m a.s.l.), over the last ca. 38 ka, using a novel combination of lake‐sediment fluxes and stable‐isotope (δ13C, δ15N, δ18O, δ30Si) data. Under glacial conditions (38.3–14.3 ka BP), high diatom productivity was maintained by substantial losses of dissolved SiO2 and soil nutrients from a sparse, leaky, terrestrial ecosystem. During the following period of enhanced monsoon rainfall and seasonality (14.3–9.5 ka BP), rapid Si cycling by fire‐prone, mesic grassland was associated with substantial aeolian transport of opal phytoliths by smoke plumes, but greatly reduced nutrient losses in runoff. Invasion of tall, subalpine shrubs after 9.5 ka BP further enhanced landscape stability, leading to very low sediment fluxes of both phytoliths and diatoms. This case study offers new insights into processes that may have operated at biome to continental scales during the late Quaternary. © Natural Environment Research Council (NERC) copyright 2008. Reproduced with the permission of NERC. Published by John Wiley &amp; Sons, Ltd.

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ 30Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ 30Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO 2 precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo ( α pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ 30Si value from roots to stem, including larger ratio of dissolved H 4SiO 4 to precipitated SiO 2 in roots than in stem. There is a positive correlation between the δ 30Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor ( α bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO 2 contents and δ 30Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ 30Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ 30Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.

Modelling the biogeochemical cycle of silicon in soils: Application to a temperate forest ecosystem

We investigated the biogeochemical cycling of silicon (Si) in an acidic brown soil covered by a coniferous forest (Douglas fir). Based on published and original data, we constructed a conceptual model and used a modified version of the reactive transport code MIN3P for model testing and quantification purposes. The model was first calibrated and further validated with respect to biomass data and Si-concentrations in capillary solutions, which were collected monthly over several years by means of suction-cup lysimeters placed at different soil depths. Following sensitivity tests, the model was calibrated quite accurately (limited to a 10% concentration error) by the adjustment of kinetic constants, longitudinal dispersion, and apparent activation energy for K-feldspar dissolution. Calibrated parameter values were constrained by ranges reported in the literature, when available. Mass balance calculations indicate that an average of 60% of the biogeochemical cycle of Si was controlled by biological processes (i.e. Si-uptake and dissolution of phytoliths). Sensitivity analyses suggest that no more than 55% of the Si-cycle is controlled by weathering of primary silicates. Such a large contribution of biological turnover to Si-cycling may be explained by the combined effects of a relatively large Si-content in the litter fall (i.e. specifically in the needles) and high biomass productivity of the coniferous species considered. In addition to potential implications for the global Si cycle, this investigation raises several fundamental questions concerning the nature of Si-uptake mechanisms and physiological use of Si by trees in natural systems.

Silicon's organic pool and biological cycle in moso bamboo community of Wuyishan Biosphere Reserve.

Biomineralization of Si by plants into phytolith formation and precipitation of Si into clays during weathering are two important processes of silicon's biogeochemical cycle. As a silicon-accumulating plant, the widely distributed and woody Phyllostachys heterocycla var. pubescens (moso bamboo) contributes to storing silicon by biomineralization and, thus, prevents eutrophication of nearby waterbodies through silicon's erosion of soil particles.A study on the organic pool and biological cycle of silicon (Si) of the moso bamboo community was conducted in Wuyishan Biosphere Reserve, China. The results showed that: (1) the standing crop of the moso bamboo community was 13355.4 g/m2, of which 53.61%, 45.82% and 0.56% are represented by the aboveground and belowground parts of moso bamboos, and the understory plants, respectively; (2) the annual net primary production of the community was 2887.1 g/(m2 x a), among which the aboveground part, belowground part, litterfalls, and other fractions, accounted for 55.86%, 35.30%, 4.50% and 4.34%, respectively; (3) silicon concentration in stem, branch, leaf, base of stem, root, whip of bamboos, and other plants was 0.15%, 0.79%, 3.10%, 4.40%, 7.32%, 1.52% and 1.01%, respectively; (4) the total Si accumulated in the standing crop of moso bamboo community was 448.91 g/m2, with 99.83% of Si of the total community stored in moso bamboo populations; (5) within moso bamboo community, the annual uptake, retention, and return of Si were 95.75, 68.43, 27.32 g/(m2 x a), respectively; (6) the turnover time of Si, which is the time an average atom of Si remains in the soil before it is recycled into the trees or shrubs, was 16.4 years; (7) the enrichment ratio of Si in the moso bamboo community, which is the ratio of the mean concentration of nutrients in the net primary production to the mean concentration of nutrients in the biomass of a community, was 0.64; and lastly, (8) moso bamboo plants stored about 1.26x10(10) kg of silicon in the organic pool made up by the moso bamboo forests in the subtropical area of China.

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of “soil” phytoliths ( p K sp 0 = 2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction ( Δ H r 25 - 80 ° C = 10.85 kJ / mol ) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for “soil” (native) and “heated” (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid–base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R = k 1 · { > SiOH 2 + } n + k 2 · { > SiOH 0 } + k 3 · { > SiO - } m , where {> i} stands for the concentration of the surface species present at the SiO 2–H 2O interface, k i are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ∼ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir, which can play an important role in the regulation of silica fluxes in terrestrial aquatic environments.

Silicon transfers in a rice field in Camargue (France)

We conducted a study of the biogeochemical cycle of silicon in a rice field in Camargue (France) in order to evaluate the role of biogenic silicon particles (BSi) in the cycle. Opal-A biogenic particles (phytoliths, diatoms…), which dissolve more rapidly than other forms of silicate usually present in soils, are postulated to represent the easiest bioavailable Si for rice. We found 0.03–0.06 wt.% of BSi in soils (mainly phytoliths). This value is lower than other values from the literature. Each year, the exportation of BSi from rice cultivation is 270 ± 80 kg Si ha − 1 . We show that BSi input by irrigation is mostly composed of diatoms and we estimate it at 100 kg Si ha − 1 year − 1 . This value is more than a third of the annual Si need for rice. The budget of the dissolved silicon (DSi) fluxes gives the following results: the atmospheric and irrigation inputs represents 1% and roughly 10%, respectively, of the annual need for rice; the drainage and infiltration outputs represent 17 ± 14 and 12 ± 9 kg Si ha − 1 year − 1 , respectively; the balance of our budget shows that at least 170 kg Si ha − 1 year − 1 are exported from the soil. If we consider the soil BSi as the only source of dissolved silicon, this stock could be exhausted in 5 years.

Aqueous reactivity of phytoliths and plant litter: Physico-chemical constraints on terrestrial biogeochemical cycle of silicon

Quantification of silicon recycling by plants is hampered by the lack of physico-chemical data on reactivity of natural phytoliths and plant litter. In this study, we used an experimental approach for determining the silica release rates of phytoliths from tropical and temperate plants (bamboos, horsetails). Results are compared with litter degradation of horsetails and pine needles. Silica release rates suggest that the reactivity of phytolith surface does not depend on topology and geometry of local structures, and does not support the existence of preferential dissolution sites on surface. Litter degradation results suggest that the silica release rate is independent of cellulose hydrolysis that implies the presence of phytoliths in an “inorganic” pool not complexed with organic matter.

Another continental pool in the terrestrial silicon cycle

Silicon is the second most abundant element on Earth. It is an important nutrient for phytoplankton and is readily absorbed by terrestrial vegetation; it also assists the removal of carbon dioxide from the atmosphere through the weathering of silicates. But the continental cycle of silicon is not well known, and only a few studies have attempted to use silicon stable isotopes (28Si, 29Si and 30Si) to quantify the continental silicon reservoirs. Dissolved silicon in sea and river waters forms a reservoir of mean isotopic value +1.1 per thousand (refs 7, 10). It is enriched in 30Si with respect to the igneous rocks reservoir, which has a mean isotopic value of -0.3 per thousand (refs 4, 9). This enrichment can only be produced by a major fractionation during weathering, and should result in the formation of a continental 30Si-depleted reservoir. Such a reservoir, however, has not been identified to date. Here we analyse silicon isotopes of in situ quartz from a sandstone series in France, using a new-generation secondary ion mass spectrometry apparatus. We show that quartz that precipitates as siliceous cements forms a strongly 30Si-depleted reservoir with isotopic values down to -5.7 per thousand, a more negative value than any previously published for terrestrial samples. Our findings suggest that quartz re-precipitation plays an important role in the biogeochemical cycle of silicon.

Ecological study of Stephanodiscus rotula during a spring diatom bloom: dynamics of intracellular elemental concentrations and correlations in relation to water chemistry, and implications for overall geochemical cycling in a temperate lake

The population of Stephanodiscus rotula in Rostherne Mere (Cheshire, UK) was studied during the spring of 1996 using light microscopy, hydrochemical analyses and scanning electron microscopy X-ray microanalysis (SEM XRMA). Data obtained were statistically analysed to reveal relationships between the elements within the cells and in the lake water. The results confirmed that algal biomass production was mainly controlled by availability of Si. The depletion of ambient Si coincided with changes in the intracellular elemental composition, particularly a considerable reduction of intracellular Si whose depletion was also reflected in changes of intracellular elemental correlations and ratios. A simple structural model of elemental relationships in S. rotula cells is proposed to explain the pattern of intracellular elemental associations. This model can be used as a reference for species response to changes in environmental parameters. S. rotula provided a significant contribution to overall biogeochemical cycling due to the removal of nutrients from the water column and transporting them to bottom sediments following the culmination of the bloom. The role of S. rotula was particularly prominent in the biogeochemical cycle of silicon, as the diatom’s spring growth may account for more than 20% of its total annual loss to bottom sediments.

Silicon cycle in the NW Mediterranean Sea: seasonal study of a coastal oligotrophic site

A study of the biogeochemical cycle of silicon has been conducted in the Gulf of Lion (NW Mediterranean) from September 1999 to September 2000. Most of the year the study site was under the influence of the NW Mediterranean Current, characterized by oligotrophic conditions. A seasonal pattern of silicon stocks was found, showing an inverse annual distribution of biogenic silica and lithogenic silica. Biogenic silica integrated stocks were higher during spring and summer (21.5 and 19.3 mmol m –2) due to siliceous phytoplankton Si uptake and build-up of biomass. By contrast lithogenic silica integrated stocks were highest during the fall and winter (61.8 and 45.0 mmol m –2), which may be explained by a higher degree of turbulence of the water column, inducing sediment resuspension. Phytoplankton counts showed that the relative contribution of diatoms to microphytoplankton at the chlorophyll a maximum averaged 51% during the study period. Si uptake rates, measured in situ from March to September 2000, were low (Σ ρSi = 0.14–1.4 mmol Si m –2 d –1) throughout the study period. Potential Si limitation of siliceous phytoplankton in the course of spring bloom development was evidenced both by Si enrichment kinetics, yielding relatively high K S values (3.46 and 4.97 μM), and by nutrient distributions, exhibiting Si exhaustion over the entire water column by mid-April. The annual integrated Si production rate amounted to 0.14 mol Si m –2 per year, one of the lowest rates reported to date, and the diatom contribution to annual carbon primary production was estimated to range between 24 and 36%. The silicon cycle at the NW Mediterranean site was similar to that observed in other oligotrophic open-ocean systems in terms of stocks, annual Si production rates, and the relative contribution of diatoms to phytoplanktonic primary production.

Ultrastructural study of the biogeochemical cycle of silicon in the soil and litter of a temperate forest

SummaryThe biogeochemical cycle of silicon is closely linked to the plant cycle. We have studied the relations between silica and organic matter during humification in a temperate deciduous forest, an acid brown soil ecosystem, the characteristics of which suggest that plants play a major role in the recycling of soluble silica. Our ultrastructural approach consists in identifying the occurrence of biogenic silica in the beech roots, in young and old beech leaves in litter and in the underlying microaggregates of the topsoil. The microaggregates were either sampled directly in situ or isolated by size fractionation.Observations of ultrathin sections by transmission electron microscopy at a micrometric scale were combined with electron energy loss microanalysis, which enabled us to identify the silica phases and their associated mineral and organic environments. Some silica deposits were identified in the cell walls of both the beech roots and the beech leaves, whereas pure silica occurred in the root cortical cells as a layer which was closely associated with polyphenolic substances. The ultrastructural study of the microaggregates showed a close association between Si‐cell wall residues and Si‐polyphenolic residues. We also identified a specific bacterial activity that seemed to be related to the degradation of siliceous cell walls. The microquartz in the topsoil showed morphological and analytical transformations that might be considered as weathering. Both ultrastructural observations and the electron energy loss microanalysis showed the presence of biogenic silica and silica‐organic material in litter and soil, and these techniques should enable us to follow the biogeochemical cycle in ecosystems and the bioavailability of silicon.