Composition, P-T parameters, and metasomatic transformations of mafic schists of the Svyatoi Nos Peninsula, Eastern Baikal Area

The paper reports data on rock and mineral compositions from the Svyatonosskaya Formation, which is a continuation of the Ol’khon Series in the northern part of the Svyatoi Nos Peninsula, eastern shore of Lake Baikal. The pyroxene-amphibole-plagioclase schists (metagabbro) are replaced there by the garnet-biotite-quartz assemblage, which was formed, according to the data of various geothermometers and calculations by the THERMOCALC computer program, under conditions corresponding to the transition from the granulite (848–811°C) to high grades of the amphibolite (715–670°C) facies under high pressures (8.7 ±1.6 kbar). In petrogenetic grids, these conditions fall onto the line of the onset of eclogitization. In nature these rocks are a continuation of the Chernorudskaya-Barakchinskaya zone of elevated pressures in the Ol’khon area. The metasomatic rocks were formed simultaneously with strike-slip faulting, when coupled zones of relatively high-(eclogite-like) and low-pressure (quartzite-marble melange) developed at the inflow of SiO₂ and K₂O and the removal of MgO and CaO. Analogous compositional changes in gneisses and schists in tectonic extension zones in Ol’khon Island and neighboring areas occurred during the development of migmatites. The migmatization of the gneisses was likely coupled with the garnetization of mafic schists in high-pressure zones and the formation of eclogite-like rocks replacing marbles. The accompanying graphitization of this block suggests that the metasomatic fluid had a hydrocarbon-hydrogen composition.     

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.     

Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Surface evolution of dissolving minerals investigated with a kinetic Ising model

In natural weathering systems, both the chemistry and the topography of mineral surfaces change as rocks and minerals equilibrate to surface conditions. Most geochemical research has focused on changes in solution chemistry over time; however, temporal changes in surface topography may also yield information about rates and mechanisms of dissolution. We use stochastic dissolution simulations of a regular 2-D lattice with reaction mechanisms defined in terms of nearest neighbor interactions to elucidate how the surface area and reactivity of a crystal evolve during dissolution. Despite the simplicity of the model, it reproduces key features observed or inferred for mineral dissolution. Our model results indicate that: (i) dissolving surfaces reach a steady-state conformation after sufficient dissolution time, (ii) linear defects cause surface area and dissolution rate to vary in concert with one another, (iii) sigmoidal and non-sigmoidal rate vs. free-energy of reaction (ΔG_rxn) behavior can be rationalized in terms of the multiple steps occurring during dissolution, and (iv) surface roughness as a function of ΔG_rxn is highly sensitive to the reaction mechanism. When simulated times to reach steady-state are compared to published time series rate data using suitable scaling, good agreement is found for silicate minerals while the model significantly over-predicts the duration of the transient for Fe and Al oxides. The implication of our simple model is that many aspects of mineral dissolution behavior, including approach to steady-state, sigmoidal vs. non-sigmoidal rate vs. ΔG_rxn behavior, and development of rougher surfaces in conditions further from equilibrium can be explained by nearest neighbor interactions and simple Kossel-type models where reactivity of a surface is defined in terms of perfect surface, step, and kink sites.     

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.     

Geochronology of Pliocene volcanism in the Dzhavakheti Highland (the Lesser Caucasus). Part 1: Western part of the Dzhavakheti Highland

Isotopic-geochronological study of the Pliocene magmatic activity in western part of the Dzhavakheti Highland (northwestern region of the Lesser Caucasus) is carried out. The results obtained imply that the Pliocene magmatic activity lasted in this part of the highland approximately 2 million years from 3.75 to 1.75–1.55 Ma. As is established, the studied volcanic rocks correspond in composition mostly to K-Na subalkaline and more abundant normal basalts. Time constraints of main phases in development of basic volcanism within the study region are figured out. We assume that individual pulses of silicic to moderately silicic volcanism presumably took place in the Dzhavakheti Highland about 3.2 and 2.5 Ma ago.     

Background concentrations of elements in surface soils and their changes as affected by agriculture use in the desert-oasis ecotone in the middle of Heihe River Basin,North-west China

The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg^− 1, Al 49.4 g kg^− 1, Fe 19.1 g kg^− 1, Ca 29.4 g kg^− 1, Mg 8.9 g kg^− 1, K 20.1 g kg^− 1, Na 17.5 g kg^− 1 and P 0.338 g kg^− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg^− 1, Mn 404.8 mg kg^− 1, Ni 17.7 mg kg^− 1, Cu 5.1 mg kg^− 1, Zn 33.7 mg kg^− 1, Pb 15.5 mg kg^− 1 and As 5.2 mg kg^− 1) and (c) other trace elements (Ti 2.0 mg kg^− 1, V 55.3 mg kg^− 1, Co 5.7 mg kg^− 1, Rb 82.4 mg kg^− 1, Sr 232.9 mg kg^− 1, Y 14.7 mg kg^− 1, Zr 194.9 mg kg^− 1, Nb 7.8 mg kg^− 1 and Ba 720.6 mg kg^− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.     

西藏冈底斯带措勤地区则弄群火山岩锆石U-Pb年代学格架及构造意义

大规模的则弄群火山岩呈带状近东西向展布于西藏冈底斯带中北部地区.对出露状况较好的措勤地区则弄群火山岩进行了锆石U-Pb定年,以建立其年代学格架便于区域对比.措勤地区则弄群火山岩多数锆石具有生长振荡环带,部分锆石显示核边结构.在措勤达雄北西部上覆于中二叠统下拉组灰岩的1件则弄群英安岩样品的LA-ICP-MS锆石U-Ph年龄为130±1Ma,1件则弄群流纹岩样品的SHRIMP锆石U-Pb年龄为129±3Ma;在措勤达雄北东部与下白垩统多尼组碎屑岩呈断层接触的1件则弄群英安岩样品中的锆石具有两组LA-ICP-MS锆石U-Pb年龄,最年轻的一组(包括增生边)为121±1Ma,较老的一组(包括核部)为131±1Ma;在措勤南西部1件则异群流纹岩样品的LA-ICP-MS锆石U-Pb年龄为111±1Ma,与措勤地区花岗岩类的侵位时代相当.这些高质量的锆石U-Pb年代学数据表明,措勤地区的则弄群火山作用很可能开始于约130Ma,停息于约110Ma,持续时间约20Ma.区域对比表明,东西延伸约1000km的则弄群火山作用同时发生在约130Ma.区域上目前的年代学数据结合同时代岩浆作用的分布特征表明,冈底斯带中北部地区早白垩世岩浆作用不太可能由新特提斯洋壳向北的低角度或平板俯冲产生.