Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ^44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ^44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ^44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.     

EXPERIMENTAL AND FIELD STUDY ON MINING-PIT MIGRATION

1 INTRODUCTION Because of the large quantity of sand and gravel in their beds, rivers have always been considered as a major source of sand and gravel for civil works. Acceptable quality, ease of extraction and economy are some of the reasons could be mentioned. Unfortunately, specific laws and regulations regarding the safe in-stream mining have not been provided for users and officials. What should be taken into account are the effects of over-mining of sand and gravel, which can cause …     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

An Automated Iridium-Strip Heater for LA-ICP-MS Bulk Analysis of Geological Samples

In this paper we describe a flux‐free fusion technique for the highly precise LA‐ICP‐MS bulk analysis of geological samples. For this purpose we have developed an automated iridium‐strip heater with temperature and melt time control. To optimise the homogeneity of the fused glasses and to reduce possible depletion of volatile elements during melting, we undertook experiments with basaltic rock and glass powders using different melting temperatures (1300–1700 °C) and melting times (5‐80 s). Major and trace element microanalysis was performed using EPMA and LA‐ICP‐MS. Homogeneous glasses were obtained for temperatures ≥ 1500 °C and melting times ≥ 10 s. High loss (20‐90%) of highly volatile elements (e.g., Cs, Ge, Sn, Pb) was observed for high melting temperatures (≥ 1600 °C) and long melting times (80 s). Standard melting conditions (1600 °C, 10 s) represent a compromise, as the glasses were homogeneous with respect to major and trace elements and, at the same time, were not depleted in elements with condensation temperatures (at a pressure of 10^?4 bar) higher than about 900 K (e.g., Zr, Hf, Ba, Sr, REE, U, Mo, Ni, Rb, Ga). Several international geological reference materials with SiO₂ ranging between 47% m/m and 59% m/m were prepared using our standard melting conditions (1600 °C, 10 s) and subsequently analysed by LA‐ICP‐MS. These samples also include the new Brazilian basaltic reference material BRP‐1. Matrix‐matched calibration of the LA‐ICP‐MS data was performed using the basaltic reference glasses KL2‐G, ML3B‐G, BCR‐2G and BHVO‐2G. Most analytical data agreed within uncertainty at the 95% confidence level with the GeoReM preferred values published in the GeoReM database for reference materials of geological and environmental interest. To demonstrate routine bulk LA‐ICP‐MS analyses of geochemical and cosmochemical samples using the whole rock fusion technique, we also present trace element data for ocean island basalts from Lanai (Hawaii) and of Martian meteorites.     

Physical modeling into outflow hydrographs and breach characteristics of homogeneous earthfill dams failure due to overtopping

The main objective of the present study is to introduce new empirical equations for the determination of breach geometrical dimensions and peak outflow discharge(Q_p).Therefore,a historic failure database of 109 embankments was collected and examined.The most important factors that affect the breach evolution,including grading size,hydraulic,and outflow characteristics are also studied.Some of the parameters used for the determination of Q_p and average breach width(Bave)have a significant effect on the erosion process,but they are less reflected in the technical literature.To study the behavior of noncohesive soils during overtopping,15 physical tests were performed at the laboratory,and the effects of interfering parameters were investigated.The experimental output hydrograph was used to simulate the hydrographs resulting from the failure of real dams,and recent artificial intelligence techniques along with linear and nonlinear regression models were employed.The area-time analysis of the laboratory hydrographs shows that the soil particle size and the characteristics of reservoir-basin significantly affect the rate of breach formation and outflow discharge.New relationships are introduced,based on the breach characteristics,by a combination of historical and experimental data,as well as case studies conducted on the hypothetical failure of 10 operational dams.The mathematical model is also used to simulate the process of breach evaluation.Based on statistical indices,comparison of the results,and sensitivity analysis,the developed equations can better express the susceptibility of materials to erosion and their application can minimize downstream vulnerabilities.     

Calcium Isotopes (δ44/40Ca) in MPI-DING Reference Glasses, USGS Rock Powders and Various Rocks: Evidence for Ca Isotope Fractionation in Terrestrial Silicates

We report δ^44/40Ca_{(SRM 915a)} values for eight fused MPI‐DING glasses and the respective original powders, six USGS igneous rock reference materials, the U‐Th disequilibria reference material TML, IAEA‐CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM‐GEOMAR and Saskatchewan Isotope Laboratory) using ⁴³Ca/⁴⁸Ca‐ and ⁴²Ca/⁴³Ca‐double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2‰ at the 95% confidence level. The impact of different preparation methods on the δ^44/40Ca_{(SRM 915a)} values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ^44/40Ca_{(SRM 915a)} values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of δ^44/40Ca_{(SRM 915a)} values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS‐1 (1.49 ± 0.06‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in ⁴⁴Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in ⁴⁴Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.     

激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用

激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一。文章介绍了多种类型的质谱仪及其使用的激光器。用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍。文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量。     

Helium loss from Martian meteorites mainly induced by shock metamorphism: Evidence from new data and a literature compilation

Abstract— Noble gas data from Martian meteorites have provided key constraints about their origin and evolution, and their parent body. These meteorites have witnessed varying shock metamorphic overprinting (at least 5 to 14 GPa for the nakhlites and up to 45–55 GPa (e.g., the lherzolitic shergottite Allan Hills [ALH] A77005), solar heating, cosmic‐ray exposure, and weathering both on Mars and Earth. Influences on the helium budgets of Martian meteorites were evaluated by using a new data set and literature data. Concentrations of ³He, ⁴He, U, and Th are measured and shock pressures for same sample aliquots of 13 Martian meteorites were determined to asses a possible relationship between shock pressure and helium concentration. Partitioning of ⁴He into cosmogenic and radiogenic components was performed using the lowest ⁴He/³He ratio we measured on mineral separates (⁴He/³He = 4.1, pyroxene of ALHA77005). Our study revealed significant losses of radiogenic ⁴He. Systematics of cosmogenic ³He and neon led to the conclusion that solar radiation heating during transfer from Mars to Earth and terrestrial weathering can be ruled out as major causes of the observed losses of radiogenic helium in bulk meteorites. For bulk rock we observed a correlation of shock pressure and radiogenic ⁴He loss, ranging between ?20% for Chassigny and other moderately shocked Martian meteorites up to total loss for meteorites shocked above 40 GPa. A steep increase of loss occurs around 30 GPa, the pressure at which plagioclase transforms to maskelynite. This correlation suggests significant ⁴He loss induced by shock metamorphism. Noble gas loss in rocks is seen as diffusion due to (1) the temperature increase during shock loading (shock temperature) and (2) the remaining waste heat after adiabatic unloading (post shock temperature). Modeling of ⁴He diffusion in the main U, Th carrier phase apatite showed that post‐shock temperatures of ?300 °C are necessary to explain observed losses. This temperature corresponds to the post‐shock temperature calculated for bulk rocks shocked at about 40 GPa. From our investigation, data survey, and modeling, we conclude that the shock event during launch of the meteorites is the principal cause for ⁴He loss.