Paleohydrogeological events recorded by stable isotopes,fluid inclusions and trace elements in fracture minerals in crystalline rock,Simpevarp area,SE Sweden

Fracture minerals calcite, pyrite, gypsum, barite and quartz, formed during several events have been analysed for δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr, trace element chemistry and fluid inclusions in order to gain knowledge of the paleohydrogeological evolution of the Simpevarp area, south-eastern Sweden. This area is dominated by Proterozoic crystalline rocks and is currently being investigated by the Swedish Nuclear Fuel and Waste Management Co. (SKB) in order to find a suitable location for a deep-seated repository for spent nuclear fuel. Knowledge of the paleohydrogeological evolution is essential to understand the stability or evolution of the groundwater system over a time scale relevant to the performance assessment for a spent nuclear fuel repository. The ages of the minerals analysed range from the Proterozoic to possibly the Quaternary. The Proterozoic calcite and pyrite show inorganic and hydrothermal-magmatic stable isotope signatures and were probably formed during a long time period as indicated by the large span in temperatures (c. 200–360 °C) and salinities (0–24 wt.% eq. CaCl₂), obtained from fluid inclusion analyses. The Paleozoic minerals were formed from organically influenced brine-type fluids at temperatures of 80–145 °C. The isotopic results indicate that low temperature calcite and pyrite may have formed during different events ranging in time possibly from the end of the Paleozoic until the Quaternary. Formation conditions ranging from fresh to brackish and saline waters have been distinguished based on calcite crystal morphologies. The combination of δ¹⁸O and crystal morphologies show that the fresh–saline water interface has changed considerably over time, and water similar to the present meteoric water and brackish seawater at the site, have most probably earlier been residing in the bedrock. Organic influence and closed system in situ microbial activity causing disequilibrium are indicated by extremely low δ¹³C (down to −99.7‰), extreme variation in δ³⁴S (−42.5‰ to +60.8‰) and trace element compositions. The frequency of calcite low in δ¹³C and high in Mn, as well as pyrite with biogenically modified δ³⁴S decreases with depth. Strontium isotopes have been useful to separate the different generations and the Sr isotope ratios in the groundwaters have been determined mainly by in situ water–rock interaction processes. The difficulty of separating late Paleozoic calcite from possibly recent calcite, and the fact that these calcites are usually found in the same fracture systems indicate that water conducting structures have been intermittently conductive from the Paleozoic and onwards. The methodology used has been successful in separating the different generations and characterising their formation conditions.     

Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

Combined stable isotope (δ¹⁸O and δ¹³C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ¹⁸O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ¹³C variability through much of the deposit reflects increasing influence of soil‐zone CO₂, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ¹⁸O values and thus show no temperature dependence. First‐order sympathetic relationships between δ¹³C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO₂ degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ¹⁸O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ¹³C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.     

全球不同构造环境蛇纹岩全岩和矿物微量元素组成及非传统稳定同位素(Fe-Zn-Cu同位素)特征

蛇纹岩对地球深部和浅部的元素循环以及氧化还原状态调节具有非常重要的作用。蛇纹岩中的流体活动性元素(fluid-mobile element, FME)是揭示地幔岩石水化、脱水以及元素循环的关键。本文系统收集和分析了前人报道的不同构造环境的蛇纹岩矿物化学、全岩微量元素和非传统稳定同位素(Fe、Zn、Cu)的组成特征,试图从多个角度总结蛇纹岩脱水过程的元素迁移规律及流体性质。蛇纹岩主要矿物蛇纹石微量元素含量具有以下主要特征：(1)不同变质程度的蛇纹岩中的蛇纹石既包含轻稀土元素(light rare earth element, LREE)富集,又包含LREE亏损的特征;(2)纤蛇纹石的REE和微量元素分布在利蛇纹石和叶蛇纹石的范围内,利蛇纹石重稀土元素(heavy rare earth element, HREE)整体上略高于叶蛇纹石且更加富集FME;(3)通过中度不相容元素与REE含量相结合,能够较好地区分橄榄石和辉石蛇纹石化所形成的蛇纹石,即辉石形成的蛇纹石富集相容元素(如Sc、Zn、Cr、Y和Ti等)并具有较高的HREE,而橄榄石形成的蛇纹石则表现为平坦且整体较低的REE分布型式。在...     

General equations for modeling fluid/rock interaction using trace elements and isotopes

General equations for modeling open and closed system fluid/rock interaction using trace elements and isotopes are presented. Taylor's (1977) open system equation for stable isotopes is extended to account for a change in the Δ value between rock and fluid during interaction. It is shown that hydrothermal systems in which fractionation factors vary during fluid/rock interaction will significantly alter the isotopic ratios of rocks compared to equivalent systems with invariant fractionation factors. The equations for modeling trace element exchange are analogous to the stable isotope equations and permit the calculation of fluid/rock ratios using changes in trace element concentrations in the rock. Similarly to stable isotope exchange, the change of the trace element concentration in a rock during infiltration is a function of the trace element concentration in the fluid, the fluid/rock partition coefficient and the fluid/rock ratio rather than simply the concentration of the trace element in the fluid.     

Metal cycling in Mesoproterozoic microbial habitats: Insights from trace elements and stable Cd isotopes in stromatolites

Reconstructing the environmental conditions that supported early life on Earth relies on well-preserved geochemical archives in the rock record. However, many geochemical tracers either lack specificity or they are affected by post-depositional alteration. We present a data set of major and trace element abundances and Cd isotope compositions of dome-shaped and conophyton-type stromatolites of the Late Mesoproterozoic Paranoá Group (Brazil), showing distinct values with unprecedented resolution at the lamina scale.The studied stromatolites consist of dolomite with a high purity and a negligible content of immobile elements (e.g., <0.66 ppm Zr), indicating that elemental compositions are not influenced by detrital contamination. Even though the carbonates have experienced different extent of recrystallization, the measured elemental and isotopic compositions do not correlate with fluid mobile elements. The stromatolites thus represent prime archives for geochemical proxies to reconstruct paleo-environmental conditions.Two endmember compositions can be distinguished by multiple proxy analysis, reflecting the contrasting depositional environments of the two types of stromatolites: Shale-normalized rare earth elements including yttrium (REY_SN) patterns of domal stromatolites show a light REY_SN (LREY) enrichment (Yb_SN/Pr_SN < 0.84), slightly super-chondritic Y/Ho ratios (33.6–39.3) and unfractionated Cd isotopes relative to upper continental crust. This indicates that the stromatolites formed in a shallow-water environment that was episodically influenced by seawater. Their REY and Cd compositions are dominated by dissolved elements that were delivered via weathering and erosion processes from the ambient continent.In contrast, REY_SN patterns of the conophyta are parallel those of modern seawater with an LREY_SN depletion relative to HREY_SN (Yb_SN/Pr_SN = 2.1 to 3.9), positive Gd_SN anomalies (1.1 to 1.4) and strong super-chondritic Y/Ho ratios (37.9 to 46.2), suggesting a microbial habitat that was dominated by seawater. Cd isotopes correlate negatively with Cd and U, but positively with Mn and Ce concentrations, reflecting authigenic carbonate formation at different depths within a redox gradient of the ancient microbial mat. ε^112/110Cd_dol values increase from −3.52 at the mat surface to +3.46 in the interior of the mat, due to the effect of kinetic fractionation during Cd-uptake, e.g. by adsorption onto organic matter or by precipitation of sulfides, in addition to incorporation into carbonate minerals. Hence, our multi-proxy approach including Cd isotopes bears a high potential to shed light on environmental conditions in ancient microbial habitats and the activity of microbial life on Early Earth.     

锆石微区原位同位素和微量元素测定的新进展

文章简述了二次离子探针质谱(SIMS)、激光剥蚀等离子体质谱(LA-ICP-MS)和激光剥蚀多接受等离子体质谱(LA-MC-ICP-MS)等3种锆石微区原位同位素和微量元素测定方法的原理和优缺点;针对U-Pb定年、铪同位素、锂同位素、多种元素的同时测定,以及仪器改进、测试方法创新、标样研发等方面的新进展进行了评述。     

Removal of trace elements from landfill leachate by calcite precipitation

Spontaneous precipitation of secondary calcite (CaCO₃) has been observed in 25 samples of landfill leachate-polluted stream waters. During the 6-month precipitation experiment, the formation of calcite acts as a principal trace-element scavenging process. The concentrations of Fe, Sr, Ba and Mn and other trace elements in solution significantly decreased as calcite formed during the experiments. The PHREEQC-2 geochemical code indicated high supersaturation of the initial leachate-polluted waters with respect to calcite. The chemical/mineralogical study (SEM/EDS, XRD, ICP MS) revealed that this newly formed calcite contains considerable amounts of metals and metalloids removed from solution. Such a geochemical process can be considered to be important for spontaneous decontamination in landfill-affected environments (stream sediments, soils) or landfill technical facilities (settling basins). This removal takes place especially during dry periods with low rain precipitation, when the landfill waters exhibit both higher alkalinity and higher trace element concentrations.     

稳定同位素和微量元素在多源多汇体系中地球化学行为的理论模拟

根据地质体系多源多汇的特点,引进了一种新的定量地球化学理论模型,适用于模拟稳定同位素和微量元素在具有多个物质来源和多种分馏途径的地质体系中的变化规律。运用本文多源多汇模型研究岩浆同化-分异结晶过程中微量元素和稳定同位素的行为,所得的结果与前人AFC模型结果一致。运用此多源多汇模型对岩浆水与大气水混合过程中结晶出的石英进行模拟计算,发现其氧同位素组成随着结晶温度的降低而变大。大气中甲烷的产生和消耗有多种途径,是一种多源多汇体系,运用此模型研究它的碳同位素组成,发现其值随着甲烷总量的增多而变大。多源多汇模型不仅从更高的层次上包含了简单分馏模式、多元混合模式和AFC模式,而且可以研究这些模式不能解决的复杂地球化学过程。     

A model for the distribution of trace elements between calcite and dolomite

A crystal-growth model is proposed, which allows ions of a trace element to enter the Ca and Mg sites of dolomite in proportion to the size of the ions relative to that of Ca and Mg ions, and which assigns equal portions of the trace element to the Ca site of dolomite and the Ca site of associated calcite. The model produces calcite/dolomite distribution coefficients of 0.79 for Mn and 0.43 for Fe, which may be compared with 0.85 and 0.28 as observed in marble, and a distribution coefficient of 2.0 for Sr and Ba, which may be compared with observed values of 2.3 for Sr and 1.8 for Ba.     

Climatic variations in MIS 11 recorded by stable isotopes and trace elements in a French tufa (La Celle,Seine Valley)

Marine Isotope Stage (MIS) 11 palaeoclimate has so far been documented in marine and ice sheet isotopic records. However, excepting some lacustrine pollen records, very little is known about palaeoclimatic conditions in continental areas. This study uses geochemical records in calcareous tufa deposits from rivers as a basis for reconstructing temperate palaeoclimatic conditions. Tufa deposits are now proven to record high‐quality palaeoclimatic information in recent to Holocene deposits. Work on older interglacial tufas is just starting and in this paper we present the first comprehensive results from a MIS 11 tufa. The tufa comes from the Seine Valley (La Celle, northern France). Geochemical data in the tufa calcite are interpreted to record primarily air temperature (δ¹⁸O) and humidity (δ¹³C and Mg/Ca and Sr/Ca). The combined data identify a warm and wet climatic optimum followed by two temperature decreases associated with oscillations in humidity. These marked climatic variations recorded through the La Celle profile are strongly coherent with the palaeoenvironmental reconstructions from malacological data. The abrupt climatic and environmental events recorded could be related to short‐term degradation of vegetation cover in Europe, which is itself controlled by global palaeoclimatic events. Copyright © 2012 John Wiley & Sons, Ltd.     

生物对环境元素和稳定同位素的选择性及研究实例

利用现代生物学最新研究成果和研究模式,对生物及其生活环境中的元素和稳定同位素之间存在的对应关系进行总结和分析认为,生物因生理、地化环境、元素形态及其利用原则等内外因子而对其生活环境中的元素和稳定同位素存在不同程度的选择性吸收、利用和富集,具体的选择性利用机制均可以从生物的形态构造直至分子水平上加以解释.当环境中元素、同位素含量发生变化时,生物因其对各元素生态幅和耐受限度的差异而并不完全对环境中化学因子的变化产生一致性的响应,分别表现为时代效应、耐受限度效应和生态幅重叠等效应等.部分生物壳体"第二层"与其围岩碳、氧同位素比值及其变化趋势保持着较好的一致性.上述认识不同程度地在泥盆纪腕足类Rhynchospirifer属和Stringocephalus属为代表的生物壳体"第二层"及其围岩的研究中得到验证.     

Meteoritic trace elements in lunar rock 14321, 184

The 16 trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Rb, Re, Sb, Se, Te, Tl and Zn) were measured by radiochemical neutron activation analysis in six samples of 14321, 184: microbreccia-2 (15), microbreccia-3 (14A, 16A and 19A), basaltic clast (1A), and light matrix material (9A). The 14321 microbreccias typically contain a siderophile-rich ancient meteoritic component, poor in volatiles, which is characterized by low $\text{Ir}\text{Au}$ and $\text{Re}\text{Au}$ ratios (0.25-0.38 and 0.34-0.50, respectively, normalized to Cl). This component also occurs in Apollo 12 KREEP glasses, norite fractions of Apollo 14 1–2 mm soils, Apennine Front breccias, and Cayley Formation material, and may represent ejecta from the Imbrian basin.The basaltic clast 14321, 184-1A closely resembles 14053 in trace element content, and both are 5–10 times higher than mare basalts in volatile trace elements (Br, Cd, Tl). The light matrix material contains 9.2 ± 0.5 per cent of microbreccias, judging from its siderophile content.     

桂岭岩体稀土、微量元素地球化学特征研究

文章运用岩石地球化学方法,对桂岭岩体的构造环境和地球化学特征进行了研究,结果显示：桂岭岩体岩石平均LREE／HREE=7．68,（La／Yb）N-6．77,（La／Sm）N-4．65,（Gd／Yb）N-1．04,平均δEu=0．45〈1,表明轻重稀土轻度分异,轻稀土相对富集,轻稀土内部分馏明显,存在负铕异常;岩体明显亏损Nb、Sr、Ti,显示桂岭岩体的源区可能主要来自地壳,是地壳环境下壳源岩石发生部分熔融的产物;研究表明,桂岭岩体形成于挤压一伸展的大地构造环境。     

The Variation of Soil Organic Matter in a Forest-Cultivation Sequence Traced by Stable Carbon Isotopes

On the basis of different photosynthetic pathways.there is an obvious difference in δ^13C values between C3 and C4 plants,In terms of this characteristic,we analyzed the organic carbon content (forestlands:1.81%-16.00%;farmland:0.45%-2.22%) and δ^13C values(forestlands:-23.86‰--27.12‰;farmland:-19.66‰--23.26‰)of three profile-soil samples either in farmland or in forestland near the Maolan Karst virgin forest,where there were developed plant C3 plants previously and now are C4 plants.Results showed that the deforestation has accelerated the decomposition rate of soil organic matter and reduced the proportion of active components in soil organic matter and thus soil fertility.     

Composition and variation of major and trace elements in Croatian bottled waters

Within the framework of the Pan-European project about the geochemistry of bottled mineral waters in Europe launched in 2007 by the European Geological Surveys (EGS) Geochemistry Expert Group fourteen brands of bottled natural waters from Croatia of both mineral and spring types were evaluated for getting more coherent spatial information about the natural variation of element concentration in bottled waters found at the European market. Results of chemical analysis show that not a single one out of fourteen analyzed bottled waters from Croatia exceeds the Croatian water standards sanctioning thereby their suitability for human consumption. Also, statistical tests performed for 41 analytes (including pH and EC) clearly show that the water chemistry is in a high degree of conformity with regional geology, depending on structural, stratigraphic and, above all, lithological diversity of aquifers. Thus Dinaric and Pannonian parts of Croatia differ largely with regard to their water types: Dinaric region is completely lacking mineral water types while, on the other side, in the Pannonian region even the spring waters show stronger mineralization in comparison with their Dinaric counterparts. Typically, all natural waters from Croatia bear the bicarbonate (HCO₃) signature. However, Ca–Mg cation pair combination is characteristic of spring waters while Na–K dominates in the mineral waters.     

Zoned calcites in Jurassic ammonite chambers: trace elements, isotopes and neomorphic origin

Zoned calcites were found in the phragmacone chambers of three Sonniniid ammonites from marine Middle Jurassic sandstones (Isle of Skye, U.K.). Each ammonite has a unique sequence of up to nine zones of calcite which fill or partially fill the chambers. Zones are defined by changes in the density of minute opaque inclusions and variation in trace-element composition. Proximal (early) calcites have undulose extinction and some exhibit the specific fabrics of fascicular-optic and radiaxial fibrous calcites. Microdolomite inclusions are found in one specimen. Early calcites, interpreted as replacements after a single isopachous fringe of acicular carbonate (probably high magnesium calcite), are succeeded by blocky ferroan calcite cement. In one specimen there are two distinct generations of calcite, in the others there is a continuous mosaic incorporating both early calcites and late cement. Isotopic composition of the early calcite zones demonstrates the initial importance of organic derived carbon (δ¹³C =— 26‰, δ¹⁸O ‰ O). Further cementation and mineralogical stabilization took place at increased temperatures and probably after modification of the pore water isotopic composition (calcites with δ¹³C =— O‰, δ¹⁸O～— 10‰). The distinctive fabrics and zonal patterns probably developed during the replacement of the precursor cement and are not primary growth features. Reversals in isotopic and trace element trends are believed to be related to the rate of neomorphic crystal growth and hence to the degree of exchange with external pore waters. Further increase in temperature, probably during Tertiary igneous activity, gave rise to the extremely light δ¹⁸O values of the late cements in the ammonite which had previously had least contact with external waters (cements with δ¹³C ～ O, δ¹⁸O ～— 20‰).     

Li isotopes and trace elements as a petrogenetic tracer in zircon: insights from Archean TTGs and sanukitoids

We report δ⁷Li, Li abundance ([Li]), and other trace elements measured by ion probe in igneous zircons from TTG (tonalite, trondhjemite, and granodiorite) and sanukitoid plutons from the Superior Province (Canada) in order to characterize Li in zircons from typical Archean continental crust. These data are compared with detrital zircons from the Jack Hills (Western Australia) with U–Pb ages greater than 3.9 Ga for which parent rock type is not known. Most of the TTG and sanukitoid zircon domains preserve typical igneous REE patterns and CL zoning. [Li] ranges from 0.5 to 79 ppm, typical of [Li] in continental zircons. Atomic ratios of (Y + REE)/(Li + P) average 1.0 ± 0.7 (2SD) for zircons with magmatic composition preserved, supporting the hypothesis that Li is interstitial and charge compensates substitution of trivalent cations. This substitution results in a relatively slow rate of Li diffusion. The δ⁷Li and trace element data constrain the genesis of TTGs and sanukitoids. [Li] in zircons from granitoids is significantly higher than from zircons in primitive magmas in oceanic crust. TTG zircons have δ⁷Li (3 ± 8‰) and δ¹⁸O in the range of primitive mantle-derived magmas. Sanukitoid zircons have average δ⁷Li (7 ± 8‰) and δ¹⁸O higher than those of TTGs supporting genesis by melting of fluid-metasomatized mantle wedge. The Li systematics in sanukitoid and TTG zircons indicate that high [Li] in pre-3.9-Ga Jack Hills detrital zircons is a primary igneous composition and suggests the growth in proto-continental crust in magmas similar to Archean granitoids.     

滇西勐兴铅锌矿床热液方解石碳氧同位素、稀土元素特征及其指示意义

勐兴铅锌矿床是滇西保山地块内系列低温热液矿床中的典型代表,但地质科研工作相对薄弱。由于方解石是该矿床中分布广泛且与热液活动息息相关的重要脉石矿物,其形成贯穿整个成矿过程,故对其C-O同位素及稀土元素组成特征进行系统研究,以便探讨矿床成矿流体来源及演化。结果显示,该矿床两阶段方解石的δ~(13)C_(PDB)和δ~(18)O_(SMOW)值与海相碳酸盐岩较为接近,且从阶段Ⅰ→阶段Ⅱ呈微弱下降趋势,表明成矿流体中的C主要来源于围岩碳酸盐岩的溶解,阶段Ⅱ成矿流体在与围岩反应之前可能已经发生CO2热液去气作用;阶段Ⅰ方解石的稀土总量、特征参数及配分模式与结晶灰岩较为一致,而阶段Ⅱ方解石与生物碎屑灰岩较为相似,表明阶段Ⅰ方解石中的REE主要来源于结晶灰岩,而后生物碎屑灰岩对阶段Ⅱ方解石中的稀土贡献较大。以上数据及其矿床地质特征均显示该矿床为MVT型铅锌矿床,结合区域构造演化,认为勐兴矿床的形成与中特提斯洋闭合后腾冲地块与保山地块陆陆碰撞挤压密切相关。     

Chromium,chromium isotopes and selected trace elements,western Mojave Desert,USA

Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ⁵³Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ⁵³Cr composition of 0‰ in the earth’s crust. Positive δ⁵³Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ⁵³Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ⁵³Cr values were observed as dissolved O₂ concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ⁵³Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ⁵³Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ⁵³Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ⁵³Cr values at the site. Although δ⁵³Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ⁵³Cr values in conjunction with major-ion data, and the δ¹⁸O and δD composition of water from wells.