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 δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si 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 SiO₂ 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 δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si 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 SiO₂ contents and δ³⁰Si 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 δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si 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.     

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

The age of the Nantuo Formation and Nantuo glaciation in South China

A U–Pb sensitive high‐resolution ion microprobe (SHRIMP) age of 654.5 ± 3.8 Ma from an ash bed immediately below the Nantuo Formation in South China provides the lowest age constraint for the Nantuo glaciation, which has been correlated with the global ‘Marinoan’ glaciation. A U–Pb SHRIMP age of 636.3 ± 4.9 Ma from a fallout tuff within the basal layer of the Nantuo Formation, along with the existing age of 635.2 ± 0.6 Ma from its overlying Doushantuo cap carbonate, suggests that the traditionally defined Nantuo Formation may have been deposited in a short time period at the end of the Nantuo glaciation. In combination with available ages globally, the data support a relatively short duration and rapid termination of ‘Marinoan’ glaciations.     

青藏高原西部赛利普中新世火山岩源区:地球化学及Sr-Nd同位素制约

青藏高原拉萨地块西部赛利普地区新生代火山岩依据主量元素可划分为超钾质、钾质和钙碱性系列,主要的岩石类型为粗面安山岩、粗面岩,一个超钾质岩石的40Ar-39Ar年龄为17.58Ma,指示出火山活动为中新世.超钾质、钾质和钙碱性火山岩都显示出富集LREE及LILE(Th、U)、亏损HFSE(Nb、Ta、Ti)的特征.超钾质火山岩具有较高的K2O(6.31%～8.55%)、MgO(6.75%～8.96%)、Cr(270.7×10-6～460.4×10-6)、Ni(142.3×10-6～233.9×10-6)含量,较高的(87Sr/86Sr)i(0.71883～0.72732)和较低的εNd(-14.78～-15.37),指示可能起源于一个前期亏损并经后期俯冲作用改造的富钾的方辉橄榄岩富集地幔源区.钾质火山岩具有比超钾质火山岩低的K2O、MgO、Cr、Ni含量以及高的Ba、Sr含量,初始87Sr/86Sr为0.71553～0.71628,初始143Nd/144Nd为0.51197～0.51198,在空间上与超钾质火山岩共生,可能是前者母岩浆的演化产物.钙碱性火山岩具有较高的Sr(881.7×10-6～1309.2×10-6)、Sr/Y比值(50～108)和较低的Y(12.05×10-6～18.02×10-6),明显亏损重稀土Yb(0.93×10-6～1.30×10-6),类似于典型的埃达克质岩成分特征但相对高钾,并具有相对低的(87Sr/86Sr);(0.70928～0.71374)以及高的εNd(-7.90～-10.91),指示起源于富钾增厚下地壳物质的部分熔融.区域上拉萨地块超钾质岩、钾质岩与N-S向地堑系在空间上共存、时间上相吻合,由此本文认为拉萨地块中新世钾质.超钾质岩和南北向地堑系的形成可能与中新世早期北向俯冲的印度大陆岩石圈断离有关.     

青藏高原东南木里地区二叠纪苦橄岩的Os-Sr-Nd同位素地球化学研究

本文报道了在青藏高原东南木里地区发现的二叠纪苦橄岩和与其共生玄武岩的主微量元素地球化学特征以及Os-Sr-Nd同位素组成。苦橄岩和与其共生玄武岩受地壳混染作用影响较小。根据苦橄岩的Ti/Y比值和初始的Os同位素组成,将木里苦橄岩分为两类:高Ti/Y型苦橄岩和低Ti/Y型苦橄岩,其中高Ti/Y型苦橄岩具有高的γ_(Os)= 5.3～ 10.7和ε_(Nd)= 5.9～ 6.4,与全球典型洋岛玄武岩的Os和Nd同位素组成接近,代表了地幔柱源区的同位素特征;而低Ti/Y型苦橄岩具有低的γ_(Os)=-4.1～ 1.2和ε_(Nd)= 3.2～ 5.0,可能表明受到了SCLM(大陆岩石圈地幔)源区物质的混染。与其共生的玄武岩具有低的γ_(Os)=-3.5～-1.6和ε_(Nd)=-0.6～ 0.7,表明其来自于不同于低Ti/Y型苦橄岩也有异于高Ti/Y型苦橄岩的地幔源区,但是也可能受到了SCLM物质的混染。基于Nd-Os同位素的地幔柱与SCLM的二端元混合模型显示:低Ti/Y型苦橄岩可能是SCLM物质组分与地幔柱起源的苦橄质原始岩浆混合形成的;与苦橄岩共生的玄武岩可能是由地幔柱来源的玄武质岩浆与SCLM小比例熔融的熔体混合形成的。     

四川大陆槽稀土矿床碳酸岩-英碱正长岩锆石U-Pb年代学和Hf同位素性质及其地质意义

川西冕宁-德昌稀土成矿带是中国最重要的稀土成矿带之一,所有稀土矿床均与碳酸岩-正长岩杂岩体有关.前人研究表明,牦牛坪、木落寨和里庄碳酸岩-碱性杂岩体成岩年龄与其相应矿床的成矿年龄基本一致,而大陆槽正长岩年龄与REE矿床的成矿年龄相差甚远.本文对大陆槽碳酸岩、英碱正长岩进行了SHRIMP U-Pb锆石年代学和LA-MC-ICPMS锆石Hf同位素原位测量,它们的形成年龄分别为12.99±0.94Ma、14.53±0.31Ma,表明两者是同时形成的,且与其成矿年龄基本一致.碳酸岩和正长岩的εHf(t)值、Hf模式年龄与它们的εNd(t)值、Nd模式年龄所展现出来的特征一致,说明在其形成过程中有地壳物质的加入.