Algal uptake of U and some other metals: Implications for global geochemical cycling

Freshwater green algae Ankistrodesmus sp, cultured in dilute solutions of metals chelated with EDTA, revealed massive uptake of U. Examination of Thames River waters and selected micro-organisms of its aquatic ecosystem revealed an average dissolved U concentration of 1.46 ppb, representing about twice the global mean riverine solute concentration of 0.6 ppb U. Suspended particulates, principally algae, contain U at 10³ to 10⁵ times that of their river habitat, averaging 28 300 ppb U. One community of the filamentous algae Spirogyra sp. contained intracellular crystals tentatively identified as the Ca-oxylate weddelite. Studies of algae from a variety of environments have shown large concentration factors for a wide range of elements. Algae from an acid U mine tailings site contain up to 2.7% U (dry weight) plus very high concentrations of other metals. Micro-organisms may act as an important sink for metal solutes in the hydrosphere.     

Ancient geochemical cycling in the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal Craton

Variations in the isotopic composition of Fe in Late Archean to Early Proterozoic Banded Iron Formations (BIFs) from the Transvaal Supergroup, South Africa, span nearly the entire range yet measured on Earth, from –2.5 to +1.0‰ in ⁵⁶Fe/⁵⁴Fe ratios relative to the bulk Earth. With a current state-of-the-art precision of ±0.05‰ for the ⁵⁶Fe/⁵⁴Fe ratio, this range is 70 times analytical error, demonstrating that significant Fe isotope variations can be preserved in ancient rocks. Significant variation in Fe isotope compositions of rocks and minerals appears to be restricted to chemically precipitated sediments, and the range measured for BIFs stands in marked contrast to the isotopic homogeneity of igneous rocks, which have δ⁵⁶Fe=0.00±0.05‰, as well as the majority of modern loess, aerosols, riverine loads, marine sediments, and Proterozoic shales. The Fe isotope compositions of hematite, magnetite, Fe carbonate, and pyrite measured in BIFs appears to reflect a combination of (1) mineral-specific equilibrium isotope fractionation, (2) variations in the isotope compositions of the fluids from which they were precipitated, and (3) the effects of metabolic processing of Fe by bacteria. For minerals that may have been in isotopic equilibrium during initial precipitation or early diagenesis, the relative order of δ⁵⁶Fe values appears to decrease in the order magnetite > siderite > ankerite, similar to that estimated from spectroscopic data, although the measured isotopic differences are much smaller than those predicted at low temperature. In combination with on-going experimental determinations of equilibrium Fe isotope fractionation factors, the data for BIF minerals place additional constraints on the equilibrium Fe isotope fractionation factors for the system Fe(III)–Fe(II)–hematite–magnetite–Fe carbonate. δ⁵⁶Fe values for pyrite are the lowest yet measured for natural minerals, and stand in marked contrast to the high δ⁵⁶Fe values that are predicted from spectroscopic data. Some samples contain hematite and magnetite and have positive δ⁵⁶Fe values; these seem best explained through production of high ⁵⁶Fe/⁵⁴Fe reservoirs by photosynthetic Fe oxidation. It is not yet clear if the low δ⁵⁶Fe values measured for some oxides, as well as Fe carbonates, reflect biologic processes, or inorganic precipitation from low-δ⁵⁶Fe ferrous-Fe-rich fluids. However, the present results demonstrate the great potential for Fe isotopes in tracing the geochemical cycling of Fe, and highlight the need for an extensive experimental program for determining equilibrium Fe isotope fractionation factors for minerals and fluids that are pertinent to sedimentary environments.     

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O₂ levels (240-380 μmol O₂/L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm²/y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2-3.3 nmol/kg (U), 7-13 nmol/kg (Mo), and 11-14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O₂ decreased, and the O₂ penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O₂ concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O₂ penetration depths.Benthic chamber experiments including the nonreactive solute tracer, Br⁻, indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment-seawater exchange due to irrigation was determined for the nonreactive tracer (Br⁻), TCO₂, , U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions.The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

勘查地球化学数据挖掘与弱异常识别

我国积累的大量高质量、多元素、多尺度的地球化学数据,为矿产勘查与环境评价提供了有效的数据支撑。如何对这些数据进行二次开发和再利用,提取有价值的地球化学异常信息并带动找矿突破,是缓解当前矿产资源短缺的重要途径之一。在覆盖区和深部的找矿实践中,由于矿体埋深和覆盖层的影响,往往在表生介质中形成弱小的地球化学异常,识别和评价弱小地球化学异常是当前勘查地球化学数据处理的重要方向之一。本文围绕地球化学异常信息的提取和评价,主要从以下几个方面讨论了相关的国内外研究进展和发展趋势:勘查地球化学数据处理与异常识别方法和模型,勘查地球化学数据闭合效应的影响及其解决方案,基于大数据和机器学习的勘查地球化学数据处理以及弱小地球化学异常的识别和评价。研究发现,在地质环境的约束下,基于大数据思维和机器学习相结合的方法,注重地球化学空间分布模式与已发现矿床的相关关系,同时使用所有地球化学变量能有效刻画具有非线性特征的地球化学空间分布模式,可识别出传统方法无法识别的异常,为开展地球化学空间模式识别与异常提取提供了新的途径。     

不同构造环境中双峰式火山岩的主要特征

总结了双峰式火山岩研究的最新进展。研究表明,双峰式火山岩可以出现在多种大地构造背景中,如大陆裂谷、洋岛、大陆拉张减薄、弧后扩张、造山后、洋内岛弧和成熟岛弧／活动陆缘等。流纹岩主要有两种成因,一种流纹岩与玄武岩来自同一源区,流纹岩通常是玄武岩浆演化的产物,出露面积相对很少,并与玄武岩具有的地球化学特征;另一种流纹岩与玄武岩不同源,流纹岩是地壳深熔作用形成的,流纹岩相比玄武岩常常是占优势的中双峰式并且     

The geochemical environment

Much of the assessment of high-level radioactive waste repositories will be accomplished through the application of geochemical models. Such models will be used to understand geochemical processes in the repository and the surrounding environment. The purpose of this paper is to review the nature of the currently available geochemical models. The kinds of calculations that a number of these models perform include aqueous speciation, mineral solubility, and mass transfer reactions. Presently, there are limitations on the success of calculation of adsorption reactions and rate-limited reactions. Ongoing development of geochemical models requires that more work be done to compile thermodynamic and kinetic data, incorporate additional geochemical processes and parameters into existing codes, and assess the accuracy of all simulations through validation studies and sensitivity analyses.     

全球地球化学填图

作指出了1973年至今世界上50余项地球化学填图计划中普遍存在的缺陷大都涉及分析问题。1988－1992年实施的国际地质对比计划IGCP259项目旨在使全世界地球化学填图方法标准化。在此项目中对分析问题提出了若干规定，主要是要求今后的填图计划应统一分析71种元素，痕量及超痕量元素的检出限必须低于相应的地壳丰度值及采用中国的GSD和加拿大的STSD标样系列，以使全球数据可以对比，在其后开始延续至今的全球地球化学填图计划IGCP360，旨在用极低密度采样早日覆盖全球大陆，讨论了正在实行的两种极低密度采样方案，并提出通过极低密度采集地极少量样品示范性实现IGCP259项目对分析要求的具体建议。     

地球化学填图的历史发展(代总序)

地球化学填图的发展属于勘查地球化学家的贡献。勘查地球化学家从发展局部矿产勘查至区域性矿产勘查,再从区域性地球化学填图至全国性乃至全球性地球化学填图。论述了西方国家、苏联和中国发展地球化学填图所走的不同道路,从而预见21世纪地球化学填图的标准化、多样化及其在解决资源与环境问题方面的重大作用。     

地球化学填图的历史发展（代总序）

地球化学填图的发展属于勘查地球化学家的贡献。勘查地球化学家从发展局部矿产勘查至区域性矿产勘查,再从区域性地球化学填图至全国性乃至全球性地球化学填图。论述了西方国家、苏联和中国发展地球化学填图所走的不同道路,从而预见21世纪地球化学填图的标准化、多样化及其在解决资源与环境问题方面的重大作用。     

Legends of geochemical maps

Analysis of geochemical maps and their legends permits the proposal of several ways of improving their information content. Firstly, coherent and comparable classification of the objects to be presented must be developed. This classification should be based on strictly defined quantitative geochemical features of the objects; natural associations, anomalous elements, rocks, ore deposits and ore-bearing areas. Secondly, the most informative features of objects must be selected and uniquely displayed with a standard set of symbols. These symbols must be clear, readily understood and logically connected. The third requirement is that maps must be prepared in accordance with the tasks they are intended to deal with, must be optimally scaled, and display only appropriate information.One possible way of meeting the above-mentioned requirements, is proposed in a system of geochemical discrimination and related map presentation methods. The latter involves black hachures for the geological base, and directed colour lines and other features of colour hachures to characterize geochemical associations. Ore deposits may be characterized on the basis of eight most meaningful features encoded in one complex hieroglyph-like symbol constructed from easily understood and memorable components. This type of construction facilitates the computerized analysis of maps and makes them far more useful for prognosis, genetic reconstruction and resource evaluation.     

多重地球化学背景下地球化学弱异常增强识别与信息提取

为对钦州湾-杭州湾成矿带(南段)庞西垌地区地球化学数据进行异常识别研究与信息提取,利用含量-面积法(C-A)得出庞西垌地区成矿主元素的异常下限,得到各元素异常分布图,并与已知矿(床)点进行叠加分析,发现已知矿(床)点与C-A法分析得到的异常区基本吻合,可根据该异常区预测未知矿床,从而为该研究区矿产资源潜力评价提供依据。为进一步从研究区复杂的地球化学背景中分离出与成矿有关的地球化学异常,采用分形滤波技术(S-A)提取致矿异常。研究表明,S-A法可在C-A法揭示的区域异常的基础上更深层次地提取出与矿化有关的局部异常用以反映研究区的多重地球化学背景,S-A法可有效地使弱异常增强进而提取出致矿异常,为庞西垌地区探寻隐伏矿体提供依据。     

The distribution, speciation and geochemical cycling of selenium in a sedimentary environment, Kesterson Reservoir, California, U.S.A.

The well-defined and intensively studied episode of Se contamination at Kesterson Reservoir (Merced County, California, U.S.A.) provided a unique opportunity to describe the distribution, speciation and geochemical transformations of Se in a variety of geochemical and ecological settings, ranging from permanent ponds to semi-arid grasslands and salt flats. Kesterson Reservoir comprises 500 ha of land contaminated with Se from agricultural drain water. In most places. Se was concentrated in surficial organic detritus and the surficial decimeter of mineral soil. At dry sites, selenate ion predominated below 20 cm depth. Elemental selenium (Se⁰) also was prominent. The amount of zero-valent Se increased slowly with time. Although selenate is thermodynamically stable in the vadose zone in the presence of oxygen, Se⁰ is an additional, metastable product of the mineralization of organic selenium. Thiols and inorganic sulfides dramatically increase the solubility of Se⁰. Decreasing pH inhibits the reaction, explaining the observed decrease in solubility and biological availability of Se in soil and aquatic systems at low pH. Adding thiols or methionine to soil increases the emission of volatile Se compounds several-fold, suggesting that thiols play a major role in the microbial cycling of Se in soil.     

化探异常定量评价

通过对地球化学特征参数、地球化学异常特征值和综合地球化学异常指标的计算,得出了6个地球化学参数:剔除比率、变异系数、浓集比率、富集系数、矿化系数、单元素地球化学异常指标及综合地球化学异常指标,用于定量评价化探异常,以供探讨。     

结合化探数据的齐石滩金矿区遥感地球化学建模

地球化学勘探找矿效果较好,但成本高、周期长;遥感地球化学利用遥感技术解决地球化学问题,遥感技术与地球化学方法相结合,可以降低找矿成本,提高效率。以新疆齐石滩金矿为研究区,将金矿成矿相关元素的化探数据与该区的WorldView-2遥感数据相结合进行遥感地球化学研究。采用多元线性回归（MLR）法建立各元素的反演模型,但反演结果精度不高,且异常位置和异常形态也存在一定的偏差,可能是混合像元致使含量与遥感影像呈非线性关系。因此,引入BP神经网络方法建模,反演精度明显提高,各元素反演异常与化探异常吻合很好,异常位置和异常形态更加精确。可见,BP神经网络方法更适合于遥感地球化学建模。     

Petrological, organic geochemical and geochemical characteristics of coal from the Soko mine, Serbia

A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter.The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C₁₅ to n-C₃₂, with an odd carbon number that predominate in almost all the samples. The contents of n-C₂₇ and n-C₂₉ alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C₂₇ to C₃₁, but without C₂₈, is typical for the Soko Banja coals.The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.     

地球化学场的连续多重分形模式

研究了粤北4292km^2内1448个基岩样品的35项元素、安徽省江南江北各约22000km^2和18100km^2内5489个和4524个水系沉积物样品的14项元素、塔里木盆地5个含油气区的7419个土壤样品的酸解烃（C1－C5）、蚀变碳酸盐、紫外、荧光等油气地球化学指标值的面积校正累计频率（ACAF）特征。研究表明，地球化学指标值的ACAF均显示连续多重分形特征，而且具两种特定模式：简单连续多重分析（SCM）模式和具高浓集的连续多重分形（HACM）模式；主要成矿元素和主要油气化探指标均不同程度地显示为HACM模式，而其他指标多表现为SCM模式。不同的分形模式可望用于区域含矿含油性和区域环境评价，而开始出现高含量叠加的“临界”含量值可能作为区域成矿成油强度的一种度量。