Geochemistry and water dynamics: II. Trace metals and Pb–Sr isotopes as tracers of water movements and erosion processes

A dynamic scheme for water movements over a flood in a small watershed was proposed in a previous paper [Ben Othman, D., Luck, J.M., Tournoud, M.G., 1997. Geochemistry and water dynamics: application to short-time scale flood phenomena in a small Mediterranean catchment: I. Alkalis, alkali-earths and Sr isotopes. Chem. Geol. [140] 9–28] based on major, alkali–alkali earth trace elements and Sr isotopes. In the present paper, metal contents and Pb isotope data are reported for the same samples, and compared to natural and anthropogenic local sources analysed for this purpose. Water treatment plants have stable but show relatively large variations, presumably related to yet unidentified (industrial?) Pb sources. Some Cu–Zn-rich chemicals used extensively on vineyards have unradiogenic around 17.7. Local rains sampled over two years show roughly similar low values. Pb from rocks is variable and more radiogenic ( ≈18.8–22.8). Except for the first hours, trace element concentrations in the dissolved load are similar to or slightly higher than those observed over the year, and similar to other moderately anthropogenic areas [Shiller, A.M., Boyle, E.A., 1987. Variability of dissolved trace metals in the Mississippi river. Geochim. Cosmochim. Acta [51] 3273–3277] for [Pb] (0.05–0.45 nM), [Zn] (10–75 nM) and [Cd] (0.03–0.18 nM). Dissolved [U] and [Co] show simple variations correlated to carbonate, related to local natural sources. Most trace elements in the particulate load are strongly correlated. Lead isotopes in the dissolved and particulate loads show ranges over the flood, again similar to those observed over the year ( ≈17.9–18.3), implying the same sources. The very good alignments observed in and vs. diagrams, especially for the particulate, are interpreted as mixing phenomena. Generally Pb isotopic signature of the dissolved load is less radiogenic than the particulate, indicating differences in sources or proportions and absence of isotopic equilibration with respect to the time of transfer. Pb isotopes shift regularly with time away from the road runoff endmember towards more radiogenic values. The strong negative correlation between Pb isotopes in the particulate load and Sr isotopes in the dissolved load, observed for the first time in a small watershed, probably reflects the local coupling between mechanical and chemical erosion, respectively.     

Persistence of pre-metamorphic C and O isotopic signatures in marbles subject to Pan-African granulite-facies metamorphism and U–Th mineralization (Tranomaro, Southeast Madagascar)

The status of fluid regimes during the Pan-African granulite-facies metamorphism in Southern Madagascar was examined by means of a mineralogical and stable isotope study of marble lithologies. In the granulitic Tranomaro area, which is made up of metasedimentary rocks (metapelitic, leptynitic (felsic) and calc–silicate metasediments) and intruded by syn-granulitic granitic bodies, syn-granulitic mineralization (Th–U) and metasomatic transformations (marbles→pyroxenites) demonstrate that fluid circulation has occurred. The Tranomaro marbles can be subdivided into two compositional groups, either Mg-poor or Mg-rich. This division reflects pre-metamorphic compositional differences rather than different histories. On a regional scale, the marbles display a large variation in (from +19 to +6.5‰ relative to SMOW) but have a more restricted range (from +1.4 to −2.5‰ relative to PDB). The lowest values are observed in magnesian marbles, whereas calcic ones do not have values lower than +13.5‰. Both initially low and high marbles may have locally been infiltrated by the syn-metamorphic fluid flow which gave rise to pyroxenites and Th–U ores (thorianite). values of carbonate in Mg-rich marbles evolve from +7 up to 8.5‰ towards the contact with a metasomatic pyroxenite in a meter-scale profile across an infiltration zone. The mineralogy, as well as the large and small-scale isotopic results argue for: (i) a pre-metamorphic origin for the isotopic variations, probably related to pre-granulitic dolomitization, (ii) a lack of pervasive fluid infiltration capable of erasing pre-metamorphic isotopic compositional differences, (iii) an absence of mantle-derived C-bearing fluids in the infiltrated zones. For the area as a whole, the present data are consistent with the decarbonation of impure siliceous limestones and dolostones coupled with fluid release from syn-metamorphic granitic intrusions.     

Carbon isotope fractionation between dissolved and gaseous carbon dioxide

Fractionation of the stable carbon isotopes between dissolved and gaseous carbon dioxide has been measured at temperature 25°C by two methods. In the first method the open system conditions and different methods of CO₂ sampling were arranged. In the second method—the closed system conditions and CO₂ gas extraction were used. The results obtained by these methods are very consistent. Gaseous CO₂ is enriched in heavy isotope by 1.03±0.02 permil in comparison to dissolved carbon dioxide.     

Carbonatation processes at the El Berrocal natural analogue granitic system (Spain): inferences from mineralogical and stable isotope studies

The El Berrocal granite/U-bearing quartz vein system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective is to understand the geochemical behaviour of natural radionuclides occurring under natural conditions. In this framework, the carbonatation processes have been studied from a mineralogical and isotopic ( and ) point of view, since carbonate anions are powerful complexing agents for U(VI) under both low-temperature hydrothermal and environmental conditions. The carbonatation processes in the system are identified by the presence of secondary ankerite, with minor calcite, scattered in the hydrothermally altered granite, and Mn calcite in fracture filling materials. The isotopic signatures of these carbonates lead us to conclude that ankerite and calcite from the former were formed at the end of the same hydrothermal process that altered the granite, at a temperature range of between 72° and 61°C for ankerite, and between 52° and 35°C for calcite. The effect of edaphic CO₂ on both carbonates, greater on calcite than on ankerite, is demonstrated. Calcites from fracture fillings are, at least, binary mixtures, in different proportions, of hydrothermal calcite, formed between 25° and <100°C, and supergenic calcite, formed at ≤25°C. According to their signatures, the effect of edaphic CO₂ in both calcites is also evident. It is assumed that: (i) hydrothermal calcite from fracture fillings and ankerite from the hydrothermally altered granite are the result of the same hydrothermal process, their chemical differences being due to the intensity of the water/rock interaction which was stronger in the altered granite than in the fractures; and (ii) all of these carbonatation processes are responsible for ancient and recent migration/retention of uranium observed in the hydrothermally altered granite and fracture fillings.     

Paleotemperatures from fluid inclusions in halite: method verification and a 100,000 year paleotemperature record, Death Valley, CA

Maximum homogenization temperatures of fluid inclusions (Th_max) in halite (laboratory-grown crystals and modern samples, Death Valley, CA) match maximum brine temperatures during halite precipitation. Maximum brine temperatures during halite precipitation in Death Valley, late April, 1993 (34.4°C) agree with Th_max (34°C) and correlate well with average maximum air temperatures in April (31.3°C) and May (37.6°C). Th_max may be used for paleoclimate interpretations based on the close relationship between saline lake temperatures and average air temperatures from modern settings. Lower homogenization temperatures, demonstrably below the temperatures at which halite grew, are interpreted to reflect collapse of some fluid inclusion walls due to the pressure difference between the inside and outside of inclusions. By only using Th_max, the problems of anomalously low homogenization temperatures due to possible collapse of fluid inclusions are avoided. Halite samples from 30 stratigraphic intervals, 90 to 0 m (100 to 0 ka), Core DV93-1, Death Valley, CA, were used to measure homogenization temperatures of fluid inclusions. Virtually all homogenization temperatures from Core DV93-1 are below the modern Th_max of 34°C (halite precipitation late April, 1993). Lacustrine halites, deposited in a perennial saline lake 35 to 10 ka, have Th_max between 19°C and 30°C, which suggests brine temperatures approximately 4°C to 15°C below modern late April values. Ephemeral saline lake halites precipitated 60 to 35 ka have Th_max between 23°C and 28°C, 6 to 11°C below modern values. The highest Th_max value in the 100 ka record (up to 35°C) is from a halite sample formed approximately 100 ka in a climate regime somewhat colder than the modern.     

Investigation of the ingrowth of radioactive daughters of in Mediterranean sapropels as a potential dating tool

Five different sapropels (S1, S3–S6) from two sites (2750 m and 3308 m water depth) in the eastern Mediterranean were analysed for C_org content and specific activities of , , and . Anoxia in the sapropel sediments during or shortly after deposition leads to U enrichment, and the observed excess of over activity is consistent with a seawater source for authigenic U. In certain cases, the U profile shape in and around the sappropels is interpreted to indicate that oxidation shortly after sapropel formation has caused a post-depositional downwards migration of both U isotopes. Systematic variability of the activity ratio across the sapropel units indicates that a different diagenetic process has also led to preferential relocation of produced in situ from the parent. The construction of quasi-isochrons in successively older sapropel units demonstrate that radioactive secular equilibrium is approached by a systematic ingrowth of over time from the marked initial disequilibrium between and the U isotopes. The effects of post-depositional diagenesis violate the isochron model boundary conditions, however, and lead to a deviation of the isochron ages from the expected stratigraphic ages. Following assessment of each data point, some improvements in the calculated ages were achieved in one case by exclusion from the calculations of those points most severely affected by open system behaviour.     

土壤理化参数的反射光谱分析

土壤可见光和近红外波段(400~2 500 nm)反射光谱信息包含了大量土壤物理化学参数,土壤反射光谱测量简单、快速,无需破坏样品,而且还可以通过高光谱遥感方法制图。文中使用江苏国土生态地球化学调查中获取的大量土壤样品,研究了土壤阳离子交换量(CEC)、有机质含量、pH值、铁氧化物类型、铁铝硅等常量元素含量等重要土壤生态地球化学参数的光谱反应。结果显示,土壤CEC是进行光谱预测非常成功的参数,1 400、1 900和2 200 nm附近一阶导数光谱(FD)值或短波方向反射率值均可以很好地反映土壤CEC的大小;土壤有机质含量、铁氧化物类型、铁铝硅含量均可以在反射率光谱或其一阶导数(FD)值找到相关波段;土壤导数光谱存在的A、B、C和D峰使反射光谱方法不仅能够定量铁氧化物总量,还能鉴别铁氧化物矿物类型(针铁矿和赤铁矿)及其相对含量;江都土壤光谱的656 nm附近FD值与pH有很大相关性,但是江苏样品显示pH值光谱经验预测具有区域依赖性,可能与土壤类型有关,说明pH与光谱参数之间的关系并非一般的线性关系,而有更复杂的机制。     

Study on the physical properties and chemical compositions of artificially synthesized coral hydroxyl apatite （CHA） bone

Abstract  

To develop synthesized coralline hydroxyl apatite (CHA) bone graft-substitute and measure its physical and chemical characteristics.     

Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

Correlation between the chemical structure of biodiesel and its physical properties

Biodiesel is a renewable, biodegradable, environmentally benign, energy efficient, substitution fuel which can fulfill energy security needs without sacrificing engine’s operational performance. Thus it provides a feasible solution to the twin crises of fossil fuel depletion and environmental degradation. The properties of the various individual fatty esters that comprise biodiesel determine the overall properties of the biodiesel fuel. In turn, the properties of the various fatty esters are determined by the structural features of the fatty acid and the alcohol moieties that comprise a fatty ester. Better understanding of the structure-physical property relationships in fatty acid esters is of particular importance when choosing vegetable oils that will give the desired biodiesel quality. By having accurate knowledge of the influence of the molecular structure on the properties determined, the composition of the oils and the alcohol used can both be selected to give the optimal performance. In this paper the relationship between the chemical structure and physical properties of vegetable oil esters is reviewed and engineering fatty acid profiles to optimize biodiesel fuel characteristics is highlighted.     

漓江源头大溶江流域土壤理化性质

文章采用ArcGIS和SPSS22.0软件分析珠江三级支流漓江上游大溶江流域内土壤pH、电导率、粒度、土壤总氮(TN)、土壤有机碳(TOC)、土壤无机碳(TIC)及其在空间上的分布特征,结果显示:(1)研究区土壤pH平均值在土下20 cm处为4.04～6.23,土下50 cm处为4.02～6.53,体现出土壤的地带性特...     

Effects of coal storage in air on physical and chemical properties of coal and on gas adsorption

This paper investigates changes in the high-volatile bituminous Lower Block Coal Member from Indiana owing to moisture availability and oxidation in air at ambient pressure and temperature over storage time. Specifically, it investigates changes in chemistry, in surface area, and pore structure, as well as changes in methane and carbon dioxide adsorption capacities. Our results document that the methane adsorption capacity increased by 40%, whereas CO₂ adsorption capacity increased by 18% during a 13-month time period. These changes in adsorption are accompanied by changes in chemistry and surface area of the coal.The observed changes in adsorption capacity indicate that special care must be taken when collecting samples and preserving coals until adsorption characteristics are measured in the laboratory. High-pressure isotherms from partially dried coal samples would likely cause overestimation of gas adsorption capacities, lead to a miscalculation of coal-bed methane prospects, and provide deceptively optimistic prognoses for recovery of coal-bed methane or capture of anthropogenic CO₂.     

青藏工程走廊热融湖塘水理化特性分析

为查明青藏工程走廊热融湖塘水理化特性及其理化特性与湖塘分布之间的关系,选取青藏工程走廊楚玛尔河至风火山段为研究区域,沿青藏公路从北向南依次选取19个热融湖塘进行水深、面积等几何特征调研并取水样,进行阴阳离子等理化参数测定。分析了热融湖塘水的理化特性,并结合调研资料探讨了热融湖塘理化特性与区域环境及湖塘分布之间的相关性。结果表明在3个研究亚区湖的水理化特性有较大差别,楚玛尔河高平原从北向南湖水矿化度逐渐升高,水质由淡水向咸水再到强咸水过渡,主要与该区域"碟"状湖的分布特征和寒旱多风及蒸发量大有关;可可西里山区和北麓河盆地的湖水矿化度较低,水质以弱咸水或淡水为主。这两个亚区湖较深,地形以丘陵盆地为主,降低了湖面的蒸发量。     

Comparison of physical and chemical properties of maceral groups separated by density dradient centrifugation

Eight coals have been selected for study of the physical and chemical properties of the maceral group . The density-gradient centrifugation technique was employed to affect maceral group separation. The maximum reflectance method of Ting and Lo was used for estimating the reflectance of very small coal particles. The reflectograms were used to characterize the separated maceral fractions. The density, elemental composition, reflectance, NMR parameters of aromaticity, protonated aromatic carbon content and ƒ_stuggereda^stuggeredH of the maceral groups were compared. Variations in the aromatic structure of the maceral groups are discussed as well as the observation that ƒ_stuggereda and ƒ_stuggereda^stuggeredH change with particle density.     

砂岩压实作用的计算机模拟及对储层物性的预测研究

通过分析学者Buryakovsky等所建立的比较成熟的沉积岩压实过程的数学模型,结合国内学者提出的砂岩压实过程的各种影响因素,应用计算机编程、根据实例数据,最终得到了比较满意的模拟结果,绘制出砂岩孔隙度、渗透率、密度随埋深的变化曲线。利用多项式拟合,建立了砂岩孔隙度、渗透率、密度与埋深的多项式方程关系式,对砂岩储层物性的预测起到了良好的指导作用。     

The physical, chemical and mineralogical properties of three cemented layers within sulfide-bearing mine tailings

The oxidation and subsequent dissolution of sulfide minerals within mine tailings impoundments releases H⁺, Fe(II), SO₄ and trace elements to the tailings pore water. Subsequent pH-buffering and hydrolysis reactions result in the precipitation of secondary phases such as gypsum, goethite and jarosite. In areas of intense precipitation, cemented layers or “hardpans” often form within the shallow tailings. Three cemented layers within pyrrhotite-bearing mine tailings at the Fault Lake, Nickel Rim and East Mine impoundments located near Sudbury, Canada, were examined. The location of the three cemented layers within the tailings stratigraphy varies as does their location relative to the water table. The morphology, mineralogy and chemical composition of the cemented layers also vary between sites. The bulk density within the three cemented layers all showed an increase relative to the surrounding uncemented tailings ranging from 9% to 29%. The porosity of each cemented layer decreased relative to the surrounding uncemented tailings ranging from an 8% to 18% decrease. The cemented layers also showed relative enrichment of total sulfur, carbon and trace elements relative to the surrounding uncemented tailings. Arsenic concentrations showed an enrichment in the cemented layers of up to 132%, Cd up to 99%, Co up to 84%, Cu up to 144%, Ni up to 693% and Zn up to 145% relative to the surrounding uncemented tailings. All the cemented layers studied show an evolution of the secondary phases with time from a gypsum–jarosite-based cement to a goethite-rich cement. The formation of these layers could potentially have a significant effect on the environmental impacts of sulfide-bearing mine waste.     

珠江口盆地坡折带特征及其对沉积体系的控制

本文基于对覆盖全区的二维地震资料研究,在珠江口盆地识别出了大型的陆架坡折及多种小型坡折带,包括侵蚀坡折带、沉积坡折带、断裂坡折带和挠曲坡折带。不同的构造背景发育了不同的坡折带类型。自30Ma年以来,坡折带总体呈向北迁移的趋势。古近纪-早中新世中期以各种小型坡折带为主,主要控制三角洲及扇三角洲等浅水沉积的展布;早中新世中期至今,由于陆架-陆坡体系已形成,坡折带以陆架坡折为主,控制了陆架边缘三角洲及海底扇等较深水沉积的发育。     

不同地貌黄土的物理力学特性和湿陷性评价

湿陷性是制约黄土场地工程建设的最主要因素。针对黄土场地现场浸水试验测试时间长、成本高等问题,在兰州新区黄土场地和靖远黄河高阶地黄土场地进行静力触探试验,研究静力触探锥尖阻力、锥侧阻力沿土层深度的变化关系,并在现场取原状黄土试样进行室内湿陷试验,研究发现室内试验所测得的自重湿陷系数沿深度具有良好的线性关系,由此建立了静力触探所测锥尖、锥侧阻力与自重湿陷系数之间的联系,提出了一种通过静力触探试验结果快速评价黄土场地自重湿陷性的方法。基于上述方法,对兰州新区和靖远黄河阶地黄土场地其他点位的测试结果进行自重湿陷性评价,验证了该方法的可行性与准确性。