Si Flux Research Articles

Dissolved silicon and its isotopes in the water column of the Bay of Bengal: Internal cycling versus lateral transport

The concentration of dissolved Si and its isotope composition are measured in the Bay of Bengal (BoB) region of the northern Indian Ocean; the isotope data are the first data set from the northern Indian Ocean. The measurements are made in eight depth profiles closely along the 87°E transect (GIO1 section of the international GEOTRACES program) and in a few samples from the northern shelf of the bay. Dissolved Si in the water column varies from ∼0.6 to ∼152.5μmol/kg, whereas the δ30Si data cover a range +1.2‰ to +3.6‰. The depth profiles of dissolved Si show generally lower values in the surface increasing with depth, whereas the pattern reverses in the case of δ30Si. These vertical distribution patterns of Si and δ30Si are similar to those reported in other oceanic regions and suggestive of the significant role of biological processes in governing Si biogeochemistry in the upper layers (top ∼1500m). In contrast, dissolved Si in near surface waters of the northern shelf and the southernmost station is exceptionally high. These results indicate a continental supply of dissolved Si from the Ganga–Brahmaputra river system (G–B) and submarine groundwater discharge (SGD) to the shelf region, and an intrusion of high salinity waters from the Arabian Sea in the southern bay. The δ30Si values of ∼1.34±0.10‰ for deep/bottom waters of the BoB (depth >1500m) are similar to those reported for the deep Southern Ocean and indicate the dominant control of water mass mixing. The dissolved Si concentrations in the bottom waters of the BoB are generally higher than those of the water mass endmembers, which suggest the need for an additional source of Si; in situ particle dissolution and/or benthic release in the central bay seem to be the potential candidate.The annual Si budget in the top ∼100m of the BoB seems to suggest that meso-scale eddies frequently occurring during non-monsoon periods can supply at the most ∼2.6gSi/m2/year, which is about 33% of the Si requirement to support new production in the bay. The supply of dissolved Si (∼1.3±0.5×1011mol/year) from the G–B river system and SGD has been calculated based on the distributions of dissolved Si concentration and δ30Si in the northern shelf waters. A comparison of this supply with the reported Si flux upstream of the estuarine zone indicates about 40% removal of dissolved Si in the G–B estuary. The mass balance of Si isotopes in the deep waters indicates that the dissolution of diatoms is the main cause of excess Si in the bay.

Vegetation impact on stream chemical fluxes: Mule Hole watershed (South India)

The proportion of chemical elements passing through vegetation prior to being exported in a stream was quantified for a forested tropical watershed (Mule Hole, South India) using an extensive hydrological and geochemical monitoring at several scales.First, a solute annual mass balance was established at the scale of the soil–plant profile for assessing the contribution of canopy interaction and litter decay to the solute fluxes of soil inputs (overland flow) and soil outputs (pore water flow as seepages). Second, based on the respective contributions of overland flow and seepages to the stream flow as estimated by a hydrological lumped model, we assigned the proportion of chemical elements in the stream that transited through the vegetation at both flood event (End Member Mixing Analysis) and seasonal scales.At the scale of the 1D soil–plant profile, leaching from the canopy constituted the main source of K above the ground surface. Litter decay was the main source of Si, whereas alkalinity, Ca and Mg originated in the same proportions from both sources. The contribution of vegetation was negligible for Na. Within the soil, all elements but Na were removed from the pore water in proportions varying from 20% for Cl to 95% for K: The soil output fluxes corresponded to a residual fraction of the infiltration fluxes. The behavior of K, Cl, Ca and Mg in the soil–plant profile can be explained by internal cycling, as their soil output fluxes were similar to the atmospheric inputs. Na was released from soils as a result of Na-plagioclase weathering and accompanied by additional release of Si. Concentration of soil pore water by evapotranspiration might limit the chemical weathering in the soil. Overall, the solute K, Ca, Mg, alkalinity and Si fluxes associated with the vegetation turnover within the small experimental watershed represented 10–15 times the solute fluxes exported by the stream, of which 83–97% transited through the vegetation. One important finding is that alkalinity and Si fluxes at the outlet were not linked to the “current weathering” of silicates in this watershed.These results highlight the dual effect of the vegetation cover on the solute fluxes exported from the watershed: On one hand the runoff was limited by evapotranspiration and represented only 10% of the annual rainfall, while on the other hand, 80–90% of the overall solute flux exported by the stream transited through the vegetation.The approach combining geochemical monitoring and accurate knowledge of the watershed hydrological budget provided detailed understanding of several effects of vegetation on stream fluxes: (1) evapotranspiration (limiting), (2) vertical transfer through vegetation from vadose zone to ground surface (enhancing) and (3) redistribution by throughfalls and litter decay. It provides a good basis for calibrating geochemical models and more precisely assessing the role of vegetation on soil processes.

Controls of DSi in streams and reservoirs along the Kaveri River, South India

There is an increasing body of evidence showing that land use may affect the concentration and flux of dissolved silica (DSi) and amorphous, biogenic Si particles (ASi/BSi) in surface waters. Here, we present a study of riverine waters collected within the Kaveri River Basin, which has a long history of land occupation with +43% population increase in the watershed during the last 30years associated with agricultural practices including canal irrigation from reservoirs and, more recently, bore well pumping. We report total dissolved solids (TDS) and suspended material (TSM) for 15 river stations and 5 reservoirs along the Kaveri itself and its main tributaries sampled during pre-monsoon, monsoon and post-monsoon periods in 2006 and 2007. The TDS in the Kaveri River globally increases from the upper reaches (humid to sub-humid climate) to the lower reaches (semi-arid climate), and at a given station from monsoon (M) to hot season (HS). The DSi concentrations range from 129μmolL−1 (M) to 390μmolL−1 (HS) in the main Kaveri stream and reaches up to 686μmolL−1 in the Shimsha River (HS). Our results indicate that DSi and the main solutes of the Kaveri River have not drastically changed since the last 30years despite the population increase. The pollution index of Van der Weijden and Pacheco (2006) ranges from 13% to 54% but DSi does not seem to be affected by domestic wastewater. ASi is mostly composed of diatoms and phytoliths that both play roles in controlling DSi. We suggest that DSi and ASi delivered to the cultivated areas through irrigation from reservoir may have two important consequences: increasing Si bioavailability for crops and limiting Si flux to the ocean.

CVD Growth of GeSnSiC Alloys Using Disilane, Digermane, Tin Tetrachloride and Methylsilane

Ge-Sn-Si-C alloys offer a large range of strain engineering which gives the possibility to tailor the material properties for advanced photonic, electronic, photovoltaic and thermoelectric applications. The benefits of Ge-Sn-Si-C alloys are possibilities to obtain a direct-to-indirect transition (for Sn-based alloys) [1], high carrier mobility [2] and low cost process [3]. In this study, Ge1-x-y-zSnxSiyCz layers (0.01≤x≤ 0.24, 0≤y≤0.12 and 0≤z≤0.01) have successfully grown on Ge and Si by using RPCVD technique. It was demonstrated that the quality of epitaxial layers is dependent on the growth parameters, layer thickness and the quality of Ge virtual layer. It was found that a proper strain balance in the matrix during the epitaxy where the Si and Si-C is adjusted carefully compared to Sn flux improves the incorporation of Sn in Ge matrix. This is explained by the compensation of tensile strain induced by Si or Si-C with the compressive strain caused by Sn in order to obtain the minimum energy in Ge matrix. Fig. 1a and 1b show RBS spectra of two GeSnSi samples when the first one has a constant Si flux whereas the sample in Fig. 1b has a graded Si flux within GeSnSi layer. The Sn incorporation improved from 3% to 24% when Si flux was graded.Incorporation of P and B in GeSnSiC matrix has been studied and the effect of dopant concentrations on Sn content has been investigated. A low boron concentration in range of 1017 cm-3 could be incorporated in the epi-layers whereas P-doping in range of 1019 cm-3could be achieved. All Ge1-x-ySnxSiyCz layers were grown at 280-330 °C at 20 torr in a RPCVD reactor. The gas precursors were Si3H8, Ge2H6, 1% B2H6 in H2, 5% PH3 in H2, and SnCl4as Si, Ge, B, P and Sn sources, respectively. The strain in the epi-layers was measured by high-resolution x-ray reciprocal lattice maps (HRRLMs). Transmission electron microscopy (TEM) was applied to detect the defects in the epi-layers and to observe the interfacial quality. The Sn, Si and C content in the samples was measured by Rutherford backscattering spectrometry (RBS) and HRRLMs. The atomic dopant concentration in the epi-layers was measured by secondary ion mass spectrometry (SIMS). Four-probe measurements were done to determine the resistivity of the doped layers.The quality of carrier and reactant gases in terms of oxygen and water vapor was investigated by residual gas analyzer (RGA). The RGA instrument was connected to the exhaust gas output and was situated in 20 mm distance from the reactant gas chamber. A RGA spectrum reveals any absorption or desorption of molecules with accuracy of ppt range. The results showed that the level of oxygen during epitaxy was as low as 10 ppb and the contamination concetration was found as low as 1017 cm-3. This low oxygen level during epitxy is due to the high purity of trisilane, digermane and tetrachloride precursors as well as the hydrogen carrier gas. Acknowledgment The Swedish Research Council (VR) is greatly acknowledged for supporting this work.

Worldwide retention of nutrient silicon by river damming: From sparse data set to global estimate

AbstractDamming of rivers represents a major anthropogenic perturbation of the hydrological cycle, with the potential to profoundly modify the availability of nutrient silicon (Si) in streams, lakes, and coastal areas. A global assessment of the impact of dams on river Si fluxes, however, is limited by the sparse data set on Si budgets for reservoirs. To alleviate this limitation, we use existing data on dissolved Si (DSi) retention by dams to calibrate a mechanistic model for the biogeochemical cycling of DSi and reactive particulate Si (PSi) in reservoir systems. The model calibration yields a relationship between the annual in‐reservoir siliceous primary productivity and the external DSi supply. With this relationship and an estimate of catchment Si loading, the model calculates the total reactive Si (RSi = DSi + PSi) retention for any given reservoir. A Monte Carlo analysis accounts for the effects of variations in reservoir characteristics and generates a global relationship that predicts the average reactive Si retention in reservoirs as a function of the water residence time. This relationship is applied to the Global Reservoirs and Dams database to estimate Si retention by damming worldwide. According to the results, dams retain 163 Gmol yr−1 (9.8 Tg SiO2 yr−1) of DSi and 372 Gmol yr−1 (22.3 Tg SiO2 yr−1) of RSi, or 5.3% of the global RSi loading to rivers.

Dynamics and drivers of the protozoic Si pool along a 10-year chronosequence of initial ecosystem states

The size and dynamics of biogenic silicon (BSi) pools influence silicon (Si) fluxes from terrestrial to aquatic ecosystems. The research focus up to now was on the role of plants in Si cycling. In recent studies on old forests annual biosilicification rates of idiosomic testate amoebae (i.e. TA producing self-secreted silica shells) were shown to be of the order of Si uptake by trees. However, no comparable data exist for initial ecosystems. We analyzed the protozoic BSi pool (idiosomic TA), corresponding annual biosilicification rates and readily available and amorphous Si fractions along a 10-year chronosequence in a post-mining landscape in Brandenburg, Germany.Idiosomic Si pools ranged from 3 to 680gSiha−1 and were about 3–4 times higher at vegetated compared to uncovered spots. They increased significantly with age and were related to temporal development of soil chemical properties. The calculation of annual biosilicification resulted in maxima between 2 and 16kgSiha−1 with rates always higher at vegetated spots. Our results showed that the BSi pool of idiosomic TA is built up rapidly during the initial phases of ecosystem development and is strongly linked to plant growth. Furthermore, our findings highlight the importance of TA for Si cycling in young artificial ecosystems.

Carbonated sediment–peridotite interaction and melting at 7.5–12GPa

Abstract To gain a better insight into deep subduction-zone processes, the interaction between model sediment and peridotite was experimentally studied using a multianvil apparatus at 7.5–12 GPa and 900–1400 °C. Two H 2 O- and CO 2 -bearing synthetic materials similar to GLOSS of Plank and Langmuir (1998) with different K/Na ratios were used. The peridotite (harzburgite) mixture consisted of natural olivine, orthopyroxene and garnet from kimberlite-derived xenoliths. Sediment (below) and peridotite (above) were packed into a Re-lined Pt capsule and exposed to constant pressure and temperature for 24–72 h. Several experiments were conducted with pure sediment mixtures. The experimental products were analyzed by EPMA and LA ICP MS. Pure sediment melting produces Ca–alkali carbonatite melts near the solidus and liquids richer in SiO 2 at high temperatures. The residual mineral assemblage is dominated by coesite/stishovite, garnet, kyanite and jadeite. Peridotite–sediment interaction results in (1) replacement of olivine in the metaperidotite zone by low-Ca pyroxene and magnesite, (2) formation of a transitional garnet-rich zone containing low-Ca pyroxene and coesite/stishovite, and (3) disappearance of kyanite and stabilization of carbonate in the metasediment layer. The peridotite zone is transformed into a low-Ca pyroxene–garnet aggregate, and its garnet/pyroxene ratio increases with increasing temperature. The sediment zone evolves with increasing temperature from coesite / stishovite + jadeite + garnet + carbonate + rutile to coesite / stishovite + jadeite + garnet. Mass transfer is dominated by Si flux from sediment to peridotite and Mg and Fe from peridotite to sediment. The composition of the melts produced in the interaction experiments differs from that from pure sediment melting in higher Mg and Si contents and much lower Ca. Trace element partition coefficients (D) between residual minerals (pyroxenes, garnet, carbonate, zircon, rutile and SiO 2 polymorphs) and melts were determined in several experiments. Modeling using the obtained D values showed that interaction with peridotite enhances REE fractionation in sediment-derived melt owing to the replacement of kyanite by garnet. The retention of jadeitic pyroxene in the transitional and metasediment zones depresses Na mobility and leads to the formation of high-K/Na liquids. The increasing stability of carbonate in the metasediment may be favorable for deep CO 2 recycling and decoupling of H 2 O and CO 2 . It was shown that the garnet–clinopyroxene residua produced by sediment–peridotite interaction and melting are similar to high-MgO diamond-bearing eclogites reported from several kimberlite pipes worldwide.

Variability of the dissolved nutrient (N, P, Si) concentrations in the Bay of Annaba in relation to the inputs of the Seybouse and Mafragh estuaries

Dissolved inorganic nitrogen (DIN), phosphate (PO4) and silicic acid (Si(OH)4) loads from the Seybouse and the Mafragh estuaries into the Bay of Annaba, Algeria, were assessed at three stations of the Bay over three years. The Seybouse inputs had high levels of DIN and PO4, in contrast to the Mafragh estuary’s near-pristine inputs; Si(OH)4 levels were low in both estuaries. The DIN:PO4 molar ratios were over 30 in most samples and the Si(OH)4:DIN ratio was less than 0.5 in the Seybouse waters, but nearly balanced in the Mafragh. The specific fluxes of Si–Si(OH)4 (400–540kgSikm−2yr−1) were comparable in the two catchments, but those of DIN were several-fold higher in the Seybouse (373kgNkm−2yr−1). The inner Bay affected by the Seybouse inputs had high levels of all nutrients, while the Mafragh plume and the outer marine station were less enriched.

The behaviour of quasar C iv emission-line properties with orientation

With a quasar sample designed for studying orientation effects, we investigate the orientation dependence of characteristics of the C IV 1549 broad emission line in approximately 50 Type 1 quasars with z=0.1-1.4. Orientation is measured for the sample via radio core dominance. In our analysis we include measurements of the continuum luminosity and the optical-to-X-ray spectral slope, spectral properties commonly included in the suite known as "Eigenvector 1", and the full-width at half maximum, full-width at one-quarter-maximum, shape, blueshift, and equivalent width of the C IV broad emission line. We also investigate a new prescription that we recently developed for predicting the velocity line width of the H-beta broad emission line based on the velocity line width of the C IV line and the ratio of continuum subtracted peak fluxes of Si IV + O IV] at 1400 A to C IV. In addition to a correlation analysis of the ultraviolet spectral properties and radio core dominance, we provide composite spectra of edge-on and face-on sources for this sample. In particular, we highlight the orientation dependence of the velocity line width predicted for H-beta. We find that this predicted line width depends on orientation in a manner similar to the true velocity line width of H-beta, where no such dependence is observed for C IV. This is an indication that orientation information concerning the line emitting regions can be extracted from ultraviolet spectra. [abridged]

Fatty acids associated with the frustules of diatoms and their fate during degradation—A case study in Thalassiosira weissflogii

Diatoms are major actors in the export of organic carbon out of the euphotic zone. Yet, the processes linking biogenic silica and carbon sedimentation fluxes to deep oceanic layers remain unclear. Analysing organic fractions in biominerals is challenging because efficient cleaning often led to structural alteration of organic molecules. Hence, although lipids are widely used as biogeochemical markers in ocean flux study, few studies have dealt with the lipids that are associated with frustules. In the present study, a protocol was set up to extract and quantify the fatty acids associated to the frustule of the diatom species Thalassiosira weissflogii. The protocol involves solvent extraction of diatom external lipids, followed by clean frustule dissolution by 4% NaOH during 1h at 95°C and subsequent solvent re-extraction of frustule-associated lipids. Results confirmed that this protocol was efficient first, to isolate the frustule from the rest of the cellular organic carbon and second to extract and quantify fatty acids (FA) associated to frustules of this species. FA composition of the frustules was significantly different from that of the whole cells consisting primarily of 14:0, 16:0 and 18:0 FA, as well as a smaller portion of 16:1 and 18:1 unsaturated FA. Frustule-associated FA constituted 7% of the total FA and 1.8% of the total POC. The 30 days T. weissflogii degradation/dissolution experiment suggested that frustule FA 14:0 and 16:0 were mainly associated with the bSiO2 phase dissolving slowly as no degradation of this pool was measured despite 78% frustule dissolution. At the end of the degradation experiment, this pool constituted 5.8% of the remaining total POC suggesting an effective protection by the frustule through strong interaction with the biogenic silica which is consistent with the correlation observed at depth between Si and POC sedimentation fluxes.

Land-use Drives Seasonal Riverine Si Cycling at the Landscape Scale

Silicon (Si) is an important element in the environment and is required for diatom production. Bedrock type, weathering rate and terrestrial vegetation are factors known to influence dissolved Si fluxes at the landscape scale, however the combined effect of these factors, along with anthropogenic influences on Si concentration and seasonal Si cycling is yet unknown. Using the provincial water quality monitoring network dataset (PWQMN) provided by the Ontario Ministry of Environment (Canada), Satellite data from The Ontario Land Cover Database (OMNR), we tested several factors that may influence dissolved silica (DSi) concentration and the annual DSi concentration range (as a proxy for seasonal cycling) for 79 river and stream monitoring stations within 53 distinct sub-watersheds in Ontario, Canada, for the years 2005 to 2011 in single and multivariate analyses. Our results indicate that the annual average DSi concentration is not affected by land-use type. The annual range in DSi, however, is positively influenced by the percent of land under agriculture, and negatively influenced by the amount of land covered by forests. Because average DSi is not affected by land-use, increased N and P loads associated with agricultural activity mean lowered Si:N and Si:P ratios in river water. Increased annual DSi range implies changes to both the timing and the quantity of Si delivered to downstream coastal environments, which may have implications for seasonal diatom production and carbon sequestration.

Silicon isotope variations in Central Siberian rivers during basalt weathering in permafrost-dominated larch forests

This work is devoted to the characterization of natural mechanisms of silicon isotope fractionation within Siberian watersheds and predicting the climate warming effect on Si fluxes from the land to the Arctic Ocean. To unravel the different sources of silica generated by basalt weathering in Central Siberia under permafrost and larch deciduous forest conditions, we measured the Si isotopic composition of large and small rivers, surface flow, interstitial soil solutions, plant litter and soils. The average annual discharge-weighted δ30Si values of the second largest tributary of the Yenissei River, Nyzhnaya Tunguska and its main northern tributary (Kochechum) are equal to 1.08±0.10‰ and 1.67±0.15‰, respectively, while their average annual Si concentrations are very similar (3.46 and 3.50mg/L, respectively). During summer baseflow, the dissolved Si isotope composition of both large rivers and a small stream ranges between 1.5 and 2.5‰. This is much heavier compared to the source basaltic rocks but similar to the fresh litter of Larix gmelinii, the dominating tree species in this region. It could be consistent with litter degradation in the uppermost soil horizons being the dominant source of solutes annually exported by Central Siberian rivers. During spring flood, accounting for 60–80% of annual Si flux, the δ30Si of the large rivers' dissolved load decreases by 1–1.5‰, thus approaching the value of the bedrock and the silicate suspended matter of the rivers (RSM). This may reflect the dissolution of the silicate suspended load at high water/mineral ratio. The winter δ30Si values of the large river dissolved load range between 1.0 and 2.5‰. During this period, contributing to ≤10% of the annual Si chemical flux, the interaction between bedrock (porous tuffs) and deep ground waters occurs at a very high solid/solution ratio, leading to the precipitation of isotopically light secondary minerals and enrichment of 30Si in the fluids that feed the river through the unfrozen flowpaths. Results of this study imply that more than a half of the silica transported by Siberian rivers may transit through the biogenic pool and that, like in other stable basaltic regions, bedrock–water interactions account for a lesser fraction of the silica flux. As a result of projected future climate warming and weathering increases in boreal regions, the δ30Si isotopic composition of large Siberian rivers is likely to shift towards less positive values.

Si cycling in a forest biogeosystem – the importance of transient state biogenic Si pools

Abstract. The relevance of biological Si cycling for dissolved silica (DSi) export from terrestrial biogeosystems is still in debate. Even in systems showing a high content of weatherable minerals, like Cambisols on volcanic tuff, biogenic Si (BSi) might contribute > 50% to DSi (Gerard et al., 2008). However, the number of biogeosystem studies is rather limited for generalized conclusions. To cover one end of controlling factors on DSi, i.e., weatherable minerals content, we studied a forested site with absolute quartz dominance (> 95%). Here we hypothesise minimal effects of chemical weathering of silicates on DSi. During a four year observation period (05/2007–04/2011), we quantified (i) internal and external Si fluxes of a temperate-humid biogeosystem (beech, 120 yr) by BIOME-BGC (version ZALF), (ii) related Si budgets, and (iii) Si pools in soil and beech, chemically as well as by SEM-EDX. For the first time two compartments of biogenic Si in soils were analysed, i.e., phytogenic and zoogenic Si pool (testate amoebae). We quantified an average Si plant uptake of 35 kg Si ha−1 yr−1 – most of which is recycled to the soil by litterfall – and calculated an annual biosilicification from idiosomic testate amoebae of 17 kg Si ha−1. The comparatively high DSi concentrations (6 mg L−1) and DSi exports (12 kg Si ha−1 yr−1) could not be explained by chemical weathering of feldspars or quartz dissolution. Instead, dissolution of a relictic, phytogenic Si pool seems to be the main process for the DSi observed. We identified canopy closure accompanied by a disappearance of grasses as well as the selective extraction of pine trees 30 yr ago as the most probable control for the phenomena observed. From our results we concluded the biogeosystem to be in a transient state in terms of Si cycling.

Silicon uptake by wheat: Effects of Si pools and pH

AbstractSilicon (Si), although not considered essential, has beneficial effects on plant growth which are mostly associated with the ability to accumulate amorphous (phytogenic) Si, e.g., as phytoliths. Phytogenic Si is the most active Si pool in the soil–plant system because of its great surface‐to‐volume ratio, amorphous structure, and high water solubility. Despite the high abundance of Si in terrestrial biogeosystems and its importance, e.g., for the global C cycle, little is known about Si fluxes between soil and plants and Si pools used by plants. This study aims at elucidating the contribution of various soil Si pools to Si uptake by wheat. As pH affects dissolution of Si pools and Si uptake by plants, the effect of pH (4.5 and 7) was evaluated. Wheat was grown on Si‐free pellets mixed with one of the following Si pools: quartz sand (crystalline), anorthite powder (crystalline), or silica gel (amorphous). Silicon content was measured in aboveground biomass, roots, and soil solution 4 times in intervals of 7 d. At pH 4.5, plants grew best on anorthite, but pH did not significantly affect Si‐uptake rates. Total Si contents in plant biomass were significantly higher in the silica‐gel treatment compared to all other treatments, with up to 26 mg g–1 in aboveground biomass and up to 17 mg g–1 in roots. Thus, Si uptake depends on the conversion of Si into plant‐available silicic acid. This conversion occurs too slowly for crystalline Si phases, therefore Si uptake from treatments with quartz sand and anorthite did not differ from the control. For plants grown on silica gel, real Si‐uptake rates were higher than the theoretical value calculated based on water transpiration. This implies that Si uptake by wheat is driven not only by passive water flux but also by active transporters, depending on Si concentration in the aqueous phase, thus on type of Si pool. These results show that Si uptake by plants as well as plant growth are significantly affected by the type of Si pool and factors controlling its solubility.

Atomistics of vapour-liquid-solid nanowire growth.

Vapour–liquid–solid route and its variants are routinely used for scalable synthesis of semiconducting nanowires, yet the fundamental growth processes remain unknown. Here we employ atomic-scale computations based on model potentials to study the stability and growth of gold-catalysed silicon nanowires. Equilibrium studies uncover segregation at the solid-like surface of the catalyst particle, a liquid AuSi droplet, and a silicon-rich droplet–nanowire interface enveloped by heterogeneous truncating facets. Supersaturation of the droplets leads to rapid one-dimensional growth on the truncating facets and much slower nucleation-controlled two-dimensional growth on the main facet. Surface diffusion is suppressed and the excess Si flux occurs through the droplet bulk which, together with the Si-rich interface and contact line, lowers the nucleation barrier on the main facet. The ensuing step flow is modified by Au diffusion away from the step edges. Our study highlights key interfacial characteristics for morphological and compositional control of semiconducting nanowire arrays.

Alloy formation during molecular beam epitaxy growth of Si-doped InAs nanowires on GaAs[111]B.

Vertically aligned InAs nanowires (NWs) doped with Si were grown self-assisted by molecular beam epitaxy on GaAs[111]B substrates covered with a thin SiO x layer. Using out-of-plane X-ray diffraction, the influence of Si supply on the growth process and nanostructure formation was studied. It was found that the number of parasitic crystallites grown between the NWs increases with increasing Si flux. In addition, the formation of a Ga0.2In0.8As alloy was observed if the growth was performed on samples covered by a defective oxide layer. This alloy formation is observed within the crystallites and not within the nanowires. The Ga concentration is determined from the lattice mismatch of the crystallites relative to the InAs nanowires. No alloy formation is found for samples with faultless oxide layers.

Inhomogeneous Si-doping of gold-seeded InAs nanowires grown by molecular beam epitaxy

We have investigated in situ Si doping of InAs nanowires grown by molecular beam epitaxy from gold seeds. The effectiveness of n-type doping is confirmed by electrical measurements showing an increase of the electron density with the Si flux. We also observe an increase of the electron density along the nanowires from the tip to the base, attributed to the dopant incorporation on the nanowire facets whereas no detectable incorporation occurs through the seed. Furthermore, the Si incorporation strongly influences the lateral growth of the nanowires without giving rise to significant tapering, revealing the complex interplay between axial and lateral growth.

Temporal dynamics of bio-available Si fluxes in a temperate forested catchment (Meerdaal forest, Belgium)

Silicon (Si) is a key element in global biogeochemical cycling and recent research has shown that changes in the biological component of the Si cycle may lead to more rapid variations in the land-ocean Si transfer than previously thought. The objective of this paper is to better understand the controls on temporal Si dynamics in terrestrial ecosystems, by studying Si fluxes from a small forested catchment in central Belgium. An intensive monitoring program (2008-2010) of dissolved and amorphous silica (DSi and ASi) concentrations and load patterns show that DSi concentrations are signif- icantly lower during winter-spring periods than during summer-autumn periods. In contrast to what was found in other studies, seasonal dynamics in Meerdaal forest are not controlled by variations in biological uptake or temperature, but mainly by the more important supply of pore-water to the groundwater table in winter-spring periods. Analysis of seasonal and event fluctuations in stream water DSi concentra- tions showed that final stream water is a mixture of old, DSi rich water pushed out of the soil, and new, DSi poor water delivered by quick flow. The mixing of old and new water finally resulted in streamwater DSi concentrations responding only moderately to varia- tions in discharge (near-chemostatic behaviour). We estimated the total DSi export from the system to be ca. 65.1 9 10 3 mol km -2 year -1 . Because Si deliv- ery is biologically regulated through an important Si cycle in the vegetation-soil continuum, an anthropo- genic (e.g. agricultural expansion) or climatic distur- bance of terrestrial ecosystems may alter both water residence times through shifts in hydrological regimes and the DSi chemical equilibrium concentration in soils. In turn, these perturbations will potentially alter long-term DSi and ASi inputs to aquatic systems.

Chrysotile dissolution rates: Implications for carbon sequestration

Serpentine minerals (e.g., chrysotile) are a potentially important medium for sequestration of CO2 via carbonation reactions. The goals of this study are to report a steady-state, far from equilibrium chrysotile dissolution rate law and to better define what role serpentine dissolution kinetics will have in constraining rates of carbon sequestration via serpentine carbonation. The steady-state dissolution rate of chrysotile in 0.1m NaCl solutions was measured at 22°C and pH ranging from 2 to 8. Dissolution experiments were performed in a continuously stirred flow-through reactor with the input solutions pre-equilibrated with atmospheric CO2. Both Mg and Si steady-state fluxes from the chrysotile surface, and the overall chrysotile flux were regressed and the following empirical relationships were obtained: FMg=-0.22pH-10.02;FSi=-0.19pH-10.37;Fchrysotile=-0.21pH-10.57 where FMg, FSi, and Fchrysotile are the log10 Mg, Si, and molar chrysotile fluxes in mol/m2/s, respectively. Element fluxes were used in reaction-path calculations to constrain the rate of CO2 sequestration in two geological environments that have been proposed as potential sinks for anthropogenic CO2. Carbon sequestration in chrysotile tailings at 10°C is approximately an order of magnitude faster than carbon sequestration in a serpentinite-hosted aquifer at 60°C on a per kilogram of water basis. A serpentinite-hosted aquifer, however, provides a larger sequestration capacity. The chrysotile dissolution rate law determined in this study has important implications for constraining potential rates of sequestration in serpentinite-hosted aquifers and under accelerated sequestration scenarios in mine tailings.

The curious case of exploding quantum dots: anomalous migration and growth behaviors of Ge under Si oxidation

We have previously demonstrated the unique migration behavior of Ge quantum dots (QDs) through Si3N4 layers during high-temperature oxidation. Penetration of these QDs into the underlying Si substrate however, leads to a completely different behavior: the Ge QDs ‘explode,’ regressing back almost to their origins as individual Ge nuclei as formed during the oxidation of the original nanopatterned SiGe structures used for their generation. A kinetics-based model is proposed to explain the anomalous migration behavior and morphology changes of the Ge QDs based on the Si flux generated during the oxidation of Si-containing layers.