Variations of δSi and Ge/Si with weathering and biogenic input in tropical basaltic ash soils under monoculture

In soils, silicon released by mineral weathering can be retrieved from soil solution through clay formation, Si adsorption onto secondary oxides and plant uptake, thereby impacting the Si-isotopic signature and Ge/Si ratio of dissolved Si (DSi) exported to rivers. Here we use these proxies to study the contribution of biogenic Si (BSi) in a soil-plant system involving basaltic ash soils differing in weathering degree under intensive banana cropping. δ³⁰Si and Ge/Si ratios were determined in bulk soils (<2 mm), sand (50-2000 μm), silt (2-50 μm), amorphous Si (ASi, 2-50 μm) and clay (<2 μm) fractions: δ³⁰Si by MC-ICP-MS Nu Plasma in medium resolution, operating in dry plasma with Mg doping (δ³⁰Si vs. NBS28 ± 0.12‰ ± 2σ_SD), Ge/Si computed after determination of Ge and Si concentrations by HR-ICP-MS and ICP-AES, respectively. Components of the ASi fraction were quantified by microscopic counting (phytoliths, diatoms, ashes). Compared to fresh ash (δ³⁰Si = −0.38‰; Ge/Si = 2.21 μmol mol⁻¹), soil clay fractions (<2 μm) were enriched in light Si isotopes and Ge: with increasing weathering degree, δ³⁰Si decreased from −1.19 to −2.37‰ and Ge/Si increased from 4.10 to 5.25 μmol mol⁻¹. Sand and silt fractions displayed δ³⁰Si values close to fresh ash (−0.33‰) or higher due to saharian dust quartz deposition, whose contribution was evaluated by isotopic mass balance calculation. Si-isotopic signatures of bulk soils (<2 mm) were strongly governed by the relative proportions of primary and secondary minerals: the bulk soil Si-isotopic budget could be closed indicating that all the phases involved were identified. Microscopic counting highlighted a surface accumulation of banana phytoliths and a stable phytolith pool from previous forested vegetation. δ³⁰Si and Ge/Si values of clay fractions in poorly developed volcanic soils, isotopically heavier and Ge-depleted in surface horizons, support the occurrence of a DSi source from banana phytolith dissolution, available for Si sequestration in clay-sized secondary minerals (clay minerals formation and Si adsorption onto Fe-oxide). In the soil-plant system, δ³⁰Si and Ge/Si are thus highly relevant to trace weathering and input of DSi from phytoliths in secondary minerals, although not quantifying the net input of BSi to DSi.     

Assessing modern arboreal phytolith sensitivity to vegetation variations in temperate forest regions

To assess the reliability of arboreal phytoliths for differentiating vegetation types in temperate forest regions, we systematically analysed arboreal leaf phytoliths from 72 arboreal plants and 49 modern soils from three forest types in northeast China. The arboreal leaf phytolith production and morphotypes were highly variable between species. The arboreal leaf phytolith assemblages could clearly distinguish between broadleaf and coniferous species, but they were much less successful in differentiating broadleaved trees into subtaxa. Coniferous leaf morphotypes were successfully used to differentiate coniferous trees into families and subtaxa, especially in the Pinaceae. Two diagnostic broadleaved and six coniferous phytolith morphotypes were recognized within the modern soil beneath forest ecosystems. These arboreal phytoliths comprised up to 10–15% of the total soil phytoliths, and were dominated by coniferous types. Arboreal phytolith concentrations and phytolith assemblages in the soils fluctuated substantially amongst the three forest types. Soil arboreal phytolith assemblages were successfully used to differentiate samples from Larix mixed forest, broadleaf forest and Pinus koraiensis mixed forest. In addition, the arboreal index quantitatively distinguished the three forest types, with B/BE values <0.4 for Larix mixed forest samples, values from 0.4 to 0.6 for broadleaf forest samples, and values from 0.6 to 0.9 for P. koraiensis mixed forest. Thus, our surface soil arboreal phytolith assemblages and arboreal index are a useful reference for differentiating forest ecotypes, and they also provide reliable analogues for arboreal phytoliths from palaeoecological contexts in temperate forest regions.     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ¹³C values of phytoliths from a C₄ grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r² < 0.3) between climate variables and the δ¹³C values of C. longifolia tissues (average δ¹³C_tissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ¹³C values are lower for grasses collected in populated areas where the δ¹³C value of atmospheric CO₂ is expected to be lower because of fossil fuel burning. Phytolith δ¹³C values are more variable (δ¹³C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ¹³C values. The strongest correlations are obtained between the δ¹³C values of stem or sheath phytoliths and humidity (r² = 0.3), latitude (r² = 0.4) and amount of precipitation (r² = 0.5). However, use of these relationships is limited by the wide spread in δ¹³C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ¹³C values of phytoliths and expected variations in the δ¹³C values of atmospheric CO₂. The C. longifolia phytoliths are depleted of ¹³C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C₃ plants. This observation may further limit the usefulness of soil-phytolith assemblage δ¹³C values for identifying shifts in grassland C₃:C₄ ratios.     

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 ( 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 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-pK 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:

     

Identifying the δO signature of precipitation in grass cellulose and phytoliths: Refining the paleoclimate model

Cellulose and silica phytoliths were extracted from the leaves and stems of Calamovilfa longifolia, a C₄ grass, grown under varying climatic conditions across the North American prairies. The oxygen-isotope compositions of both cellulose and silica record a complex signal of the isotopic composition of the soil water that feeds the plants and the relative humidity conditions that influence transpiration rates, stomatal conductance, and ultimately the ¹⁸O-enrichment of leaf water. As the initial stages of cellulose formation occur in the leaves, cellulose in both the leaves and stems forms primarily from leaf water and does not differ greatly in its oxygen-isotope composition between these locations. In contrast, the δ¹⁸O values of leaf phytoliths are significantly enriched in ¹⁸O relative to stem phytoliths, reflecting the varying isotopic composition of the water in these tissues. The oxygen-isotope compositions of leaf cellulose may be used as a proxy for the isotopic composition of water involved in leaf phytolith formation, while the δ¹⁸O values of stem phytoliths can be used to determine the δ¹⁸O values of stem water involved in partial exchange reactions during the transport of carbohydrates through the plant. A comparison of the isotopic compositions of phytoliths with cellulose allows for the deduction of soil and leaf water δ¹⁸O values as well as temperature and relative humidity conditions during plant growth. This approach has application in paleoclimate studies that traditionally have required estimations of one or more of these variables because direct measurements were unavailable.     

Simultaneous thin section and phytolith observations of finely stratified deposits from Neolithic Çatalhöyük,Turkey: implications for paleoeconomy and Early Holocene paleoenvironment

Simultaneous thin section and phytolith observations of finely stratified anthropogenic deposits from the Neolithic settlement of Çatalhöyük, Turkey, dated between 7400 and 6000 BC provide evidence for both the depositional context and phytolith assemblage of these deposits. Although extracted phytoliths provide a general picture of vegetation that supports existing evidence of a local wet marshland environment, comparisons with observations of phytoliths in situ indicate a diverse range of microcontexts, as well as depositional and post‐depositional processes that influence phytolith size. This has implications for studies that use conjoined phytolith size as a proxy for water availability and early agricultural practices. Observations indicate a significant background noise of phytoliths and micro‐charcoal in the deposits, linked to the frequent use of fire, which has implications for interpreting assemblages where phytolith counts are low, such as from floors of buildings. This study confirms the usefulness of phytoliths in providing information on human plant use and environment where the taphonomy of the deposits is clear, and provides new evidence for wet farming of at least some of the wheat found at the site. It also suggests there needs to be greater consideration of phytolith taphonomy, which can be provided to an extent by combining phytolith analysis with thin section micromorphology. Copyright © 2011 John Wiley & Sons, Ltd.     

植硅体在河流硅输送中的作用

高等植物产生的植硅体是古气候和古环境研究的重要手段,也是陆地硅循环中重要的硅的储库;植硅体通过河流的跨区域输送在全球硅的生物地球化学循环中起着重要作用,是区域硅循环研究的重要载体,然而这方面的关注却很少。河流输送的生物硅大致分为自源和异源两种类别。"自源"生物硅主要包括河流水体本身自生浮游植物(主要是淡水硅藻)产生的硅质颗粒;"异源"生物硅主要由流域土壤的侵蚀输出到河流的植硅体所构成。流域地表过程是使得部分土壤中的植硅体进入河流的主要途径,并成为河流生物硅输送中重要的形式,这对河流-河口水循环体系的硅生物地球化学循环过程产生了重要的影响,但人们对河流输送的植硅体在硅循环中的作用的研究还不够。文章着眼于陆海相互作用研究,以河流中水体携带的植硅体为中心,总结了河流植硅体输送在地表水体硅循环系统中贡献的研究进展,分析了长江与黄河植硅体入海通量与河口行为及对近海海洋环境的影响。最后,对未来河流输送的植硅体参与硅循环研究可能需要加强的科学问题提出了建议。     

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.     

Exploring sustainability of aquifers based on predictive modeling of sorption characteristics of arsenic enriched Holocene sediments in Bangladesh

The importance of accessing safe aquifers in areas with high As is being increasingly recognized. The present study aims to investigate the sorption and mobility of As at the sediment-groundwater interface to identify a likely safe aquifer in the Holocene deposit in southwestern Bangladesh. The upper, shallow aquifer at around 18 m depth, which is composed mainly of very fine, grey, reduced sand and contains 24.3 μg/g As, was found to produce highly enriched groundwater (190 μg/L As). In contrast, deeper sediments are composed of partly oxidized, brownish, medium sand with natural adsorbents like Fe- and Al-oxides; they contain 0.76 μg/g As and impart low As concentrations to the water (4 μg/L). These observations were supported by spectroscopic studies with SEM, TEM, XRD and XRF, and by adsorption, leaching, column tests and sequential extraction. A relatively high in-situ dissolution rate (R_r) of 1.42 × 10⁻¹⁶ mol/m²/s was derived for the shallower aquifer from the inverse mass-balance model. The high R_r may enhance As release processes in the upper sediment. The field-based reaction rate (K_r) was extrapolated to be roughly 1.23 × 10⁻¹³ s⁻¹ and 6.24 × 10⁻¹⁴ s⁻¹ for the shallower and deeper aquifer, respectively, from the laboratory-obtained adsorption/desorption data. This implies that As is more reactive in the shallower aquifer. The partition coefficient for the distribution of As at the sediment-water interface (K_d-As) was found to range from 5 to 235 L/kg based on in-situ, batch adsorption, and flow-through column techniques. Additionally, a parametric equation for K_d-As (R² = 0.67) was obtained from the groundwater pH and the logarithm of the leachable Fe and Al concentrations in sediment. A one-dimensional finite-difference numerical model incorporating K_d and K_r showed that the shallow, leached As can be immobilized and prevented from reaching the deeper aquifer (∼150 m) after 100 year by a natural filter of oxidizing sand and adsorbent minerals like Fe and Al oxides; in this scenario, 99% of the As in groundwater is reduced. The deeper aquifer appears to be an adequate source of sustainable, safe water.     

Experimental study of terrestrial plant litter interaction with aqueous solutions

Quantification of silicon and calcium recycling by plants is hampered by the lack of physico-chemical data on reactivity of plant litter in soil environments. We applied a laboratory experimental approach for determining the silica and calcium release rates from litter of typical temperate and boreal plants: pine (Pinus laricio), birch (Betula pubescens), larch (Larix gmelinii), elm (Ulmus laevis Pall.), tree fern (Dicksonia squarrosa), and horsetail (Equisetum arvense) in 0.01 M NaCl solutions, pH of 2-10 and temperature equals to 5, 25 and 40 °C. Open system, mixed-flow reactors equipped with dialysis compartment and batch reactors were used. Comparative measurements were performed on intact larch needles and samples grounded during different time, sterilized or not and with addition or not of sodium azide in order to account for the effect of surface to mass ratio and possible microbiological activity on the litter dissolution rates. Litter degradation results suggest that the silica release rate is independent on dissolved organic carbon release (cell breakdown) which implies the presence of phytoliths in a pure “inorganic” pool not complexed with organic matter. Calcium and DOC are released at the very first stage of litter dissolution while Si concentration increases gradually suggesting the presence of Ca and Si in two different pools. The dry-weight normalized dissolution rate at circum-neutral pH range (approx. 1-10 μmol/g_DW/day) is 2 orders of magnitude higher than the rates of Si release from common soil minerals (kaolinite, smectite, illite). Minimal Ca release rates evaluated from batch and mixed-flow reactors are comparable with those of most reactive soil minerals such as calcite and apatite, and several orders of magnitude higher than the dissolution rates of major rock-forming silicates (feldspars, pyroxenes). The activation energy for Si liberation from plant litter is approx. 50 kJ/mol which is comparable with that of surface-controlled mineral dissolutions. It is shown that the Si release rate from the above-ground forest biomass is capable of producing the Si concentrations observed in soil solutions of surficial horizons and contribute significantly to the Si flux from the soil to the river.     

Fractionation,distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district,Guizhou Province,Southwestern China: Part 2 – Methylmercury

Water samples were collected during normal flow (2007) and during a drought period (2008) from five rivers and tributaries draining the Wanshan Hg mining district, Guizhou, China. Unfiltered methylmercury (MeHg) as well as particulate and dissolved fractions of MeHg (P-MeHg, D-MeHg) were measured to assess the spatial and temporal variation of MeHg contamination in the local river system. Most locations (about 80%) displayed higher MeHg concentrations during drought period than during normal discharge conditions. Concentrations of MeHg during the drought period ranged from <0.035 to 11 ng L⁻¹ (geometric mean: 0.43), while during normal flow the concentrations ranged from <0.035 to only 3.4 ng L⁻¹ (geometric mean: 0.21). Concentrations of MeHg were positively correlated with total Hg (THg) concentrations (R² = 0.20–0.58, P < 0.001) and inversely related to distance from the calcines, during both sampling periods (R² = 0.34 and 0.23, P < 0.001, for low and normal flow, respectively) indicating that calcines may be important sources of MeHg to the downstream environment. Approximately 39% of MeHg was bound to particulates and the rest was transported in the dissolved phase along stretches of the entire river, which was different from THg, as this was mainly transported bound to particulates (commonly more than 80%).     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Biogenic silica in wetlands and their relationship with soil and groundwater biogeochemistry in the Southeastern of Buenos Aires Province,Argentina

Although phytoliths constitute part of the wetland suspended load, there are few studies focused on the quantification of them in the biogenic silica (BSi) pool. So, the aim of this paper is both to determine BSi content (diatoms and phytoliths) and its relationship with dissolved silica in surface waters, and the influence of soil and groundwater Si biogeochemistry in Los Padres wetland (Buenos Aires Province, Argentina). In the basin of the Los Padres wetland, dissolved silica (DSi) concentration is near 840 ± 232 μmol/L and 211.83 ± 275.92 μmol/L in groundwaters and surface waters, respectively. BSi represents an 5.6–22.1% of the total suspension material, and 8–34% of the total mineralogical components of the wetland bottom sediments. DSi and BSi vary seasonally, with highest BSi content (diatoms specifically) during the spring–summer in correlation to the lowest DSi concentration. DSi (660–917.5 μmol/L) and phytolith (3.35–5.84%) concentrations in the inflow stream are higher than in the wetland and its outflow stream (19.1–113 μmol/L; 0.45–3.2%, respectively), probably due to the high phytolith content in soils, the high silica concentration in the soil solution, and the groundwater inflow. Diatom content (5–16.8%) in the wetland and its outflow stream is higher than in the inflow stream (0.45–1.97%), controlling DSi in this system. The understanding of the groundwater–surface water interaction in an area is a significant element for determining the different components and the role that they play on the local biogeochemical cycle of Si.     

植硅体化学组成研究进展

现代植物植硅体化学组成研究有利于揭示植硅体的化学组成与细胞形态、植物种类及植物生长环境之间的关系,认识植硅体形成机制、植物分类及生态意义。植硅体化学组成测试方法多种多样,主要涉及植硅体化学元素组成及Si、O和C元素同位素组成测定,研究表明植硅体主要含二氧化硅和水,封闭有少量的有机成分及多种矿质元素。在植硅体封闭有机成分存在形式,部分元素的形成、迁移等循环机理,稳定碳同位素组成、分布及其生态指示意义以及^14C测年研究等方面取得一定认识。植物种类、组织部位、细胞微环境以及植物生长的环境因子能够影响植硅体的化学组成。植硅体化学组成研究对植硅体形成机制及碳、硅等元素循环具有重要意义,植硅体部分化学元素、植硅体稳定同位素组成及^14C测年具有较好的古环境及考古研究潜力。现代植物植硅体化学组成及其与环境因子的关系,以及植硅体电子探针微区研究有待于进一步深入开展。     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

Phytolith reference study for identifying vegetation changes in the forest−grassland region of northeast China

To provide a basis for tracing changes in vegetation and tree cover density, we studied the phytoliths of 129 common temperate plant species, and extracted the phytoliths from 75 surface soil samples from sites in grassland, forest−grassland ecotone and forest habitats in northeast China. From the analysis of shapes and morphological parameters of the plant samples, we developed a reference data set of herbaceous and woody phytoliths, and subsequently identified 21 herbaceous and 13 woody phytolith types in the surface soil samples. To test the reliability of soil phytolith analysis for distinguishing forest, grassland and the forest−grassland ecotone, we used principal components analysis (PCA) and discriminant analysis (DA) to summarize the soil phytolith assemblage characteristics of the different ecosystems. The results show that the grassland and forest samples are characterized by abundant herbaceous and woody phytoliths, respectively; and that forest−grassland ecotone habitats are characterized by low abundances of blocky polyhedral, multifaceted epidermal and sclereid phytoliths. In general, the surface soil phytolith assemblages can reliably differentiate samples from forest, grassland and the forest−grassland ecotone, with up to 92% of the samples classified correctly. We also tested the reliability of phytolith indices (W/G (1), W/G (2), W/G (3)) for discriminating different vegetation types in our study area, and found that W/G (2) was the most reliable index and corresponded well with the species inventory data. The W/G values for grassland ranged from 0 to 0.3, from 0.3 to 0.6 for the forest−grassland ecotone, and exceeded 0.6 for forest. We conclude that our study provides reliable analogues for phytolith assemblages from palaeoecological contexts, which can be used to reconstruct shifts in forest−grassland ecotones and vegetation succession in temperate areas.     

Vent fluid chemistry of the Rainbow hydrothermal system (36°N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes

The Rainbow hydrothermal field is located at 36°13.8′N-33°54.15′W at 2300 m depth on the western flank of a non-volcanic ridge between the South AMAR and AMAR segments of the Mid-Atlantic Ridge. The hydrothermal field consists of 10-15 active chimneys that emit high-temperature (∼365 °C) fluid. In July 2008, vent fluids were sampled during cruise KNOX18RR, providing a rich dataset that extends in time information on subseafloor chemical and physical processes controlling vent fluid chemistry at Rainbow. Data suggest that the Mg concentration of the hydrothermal end-member is not zero, but rather 1.5-2 mmol/kg. This surprising result may be caused by a combination of factors including moderately low dissolved silica, low pH, and elevated chloride of the hydrothermal fluid. Combining end-member Mg data with analogous data for dissolved Fe, Si, Al, Ca, and H₂, permits calculation of mineral saturation states for minerals thought appropriate for ultramafic-hosted hydrothermal systems at temperatures and pressures in keeping with constraints imposed by field observations. These data indicate that chlorite solid solution, talc, and magnetite achieve saturation in Rainbow vent fluid at a similar pH_(T,P) (400 °C, 500 bar) of approximately 4.95, while higher pH values are indicated for serpentine, suggesting that serpentine may not coexist with the former assemblage at depth at Rainbow. The high Fe/Mg ratio of the Rainbow vent fluid notwithstanding, the mole fraction of clinochlore and chamosite components of chlorite solid solution at depth are predicted to be 0.78 and 0.22, respectively. In situ pH measurements made at Rainbow vents are in good agreement with pH_(T,P) values estimated from mineral solubility calculations, when the in situ pH data are adjusted for temperature and pressure. Calculations further indicate that pH_(T,P) and dissolved H₂ are extremely sensitive to changes in dissolved silica owing to constraints imposed by chlorite solid solution-fluid equilibria. Indeed, the predicted correlation between dissolved silica and H₂ defines a trend that is in good agreement with vent fluid data from Rainbow and other high-temperature ultramafic-hosted hydrothermal systems. We speculate that the moderate concentrations of dissolved silica in vent fluids from these systems result from hydrothermal alteration of plagioclase and olivine in the form of subsurface gabbroic intrusions, which, in turn are variably replaced by chlorite + magnetite + talc ± tremolite, with important implications for pH lowering, dissolved sulfide concentrations, and metal mobility.     

Mineralogical and textural variation of silica minerals in hydrothermal flow-through experiments: Implications for quartz vein formation

We conducted hydrothermal flow-through experiments at 430 °C and 31 MPa to investigate the mechanism of silica precipitation on granite under crustal conditions. Two experiments were performed using different input solutions: a single-component Si solution, and a multi-component solution with minor Al, Na, and K. The degree of supersaturation with respect to quartz, Ω = C_Si/C_Si,Qtz,eq, where C_Si and C_Si,Qtz,eq indicate Si concentration in solutions and the solubility of quartz within water, respectively, decreased from 3-3.5 to <1.1 along the flow path. A variety of silica minerals formed during the experiments (opal-A, opal-C, chalcedony, and quartz), and their occurrences and modal abundances changed in response to Ω and the presence of additives in the solution.For near-equilibrium solutions (Ω < ∼1.2), silica precipitation occurred in a simple way in both experiments, being restricted to overgrowths on pre-existing quartz surfaces in the granite. At higher saturation levels (Ω > ∼1.2), silica minerals were deposited on other surfaces in addition to quartz. In the single-component experiment, the dominant silica minerals changed in the order of opal-A → opal-C → quartz with decreasing Si concentration along the flow path. In contrast, in the multi-component experiment, quartz and minor chalcedony formed throughout the entire reaction vessel. This finding indicates that impurities (Na, K, and Al) in the solutions inhibited the precipitation of opal and enhanced the direct nucleation of quartz. The systematic appearance of metastable silica minerals were examined by nucleation processes and macroscopic precipitation kinetics. Our experimental results indicate that different precipitation mechanisms yield contrasting textures, which in turn suggests that vein textures can be used as indicators of solution chemistry within the fracture.     

Ovi-caprid dung as an indicator of paleovegetation and paleoclimate in northwestern China

Diverse palynomorphs and phytoliths recovered from coprolites of ovi-caprids (sheep, goat) collected from Yang-Hai Tomb at Xinjiang Province, China, have been used to elucidate the dietary pattern of ancient livestock and to reconstruct the paleovegetation and paleoclimate of this part of northwest China ca. 2500 ¹⁴C yr BP. Palynological and phytolith data suggest that a rich dry temperate vegetation prevailed in the area during the said period. Climatic conditions and grassland vegetation type of the area are explored using phytolith indices.     

Re-assessing the surface cycling of molybdenum and rhenium

We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg⁻¹ (Mo), and 16.5 pmol kg⁻¹ (Re, natural + anthropogenic). The linear relationship of dissolved Re and in global rivers (R² = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg⁻¹. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03-5.9 pmol kg⁻¹), and the nmol kg⁻¹ level Re concentrations of mine waters. The linear Mo- relationship (R² = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10⁵ yr (τ_Mo) and 1.3 × 10⁵ yr (τ_Re, pre-anthropogenic).