Fracture zone-scale variation of trace elements and stable isotopes in calcite in a crystalline rock setting

With an aim to increase the understanding about the isotopic and chemical heterogeneity of calcites in water-conducting fracture zones with different crystalline wall rock compositions at different depths, we present trace element chemistry, isotopic composition (δ¹⁸O, δ¹³C, ⁸⁷Sr/⁸⁶Sr) and biomarkers of euhedral low-temperature fracture-coating calcite. Paleohydrogeological fluctuations and wall rock influence on the hydrochemistry in the deep groundwater are explored. Samples are from several fracture zone sub-fractures (at −360 to −740 m), retrieved during an extensive core drilling campaign in Sweden.Calcite generally showed fracture zone specific values of δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr, which indicates precipitation from relatively homogeneous fluid (similar to the modern groundwater at the site) at the same event in each fracture zone. δ¹⁸O and δ¹³C in the different fracture zones were consistent with precipitation from waters of different salinity and decreasing organic input with depth, respectively. The latter is also supported by biomarkers showing clear indications of SRB-related organic compounds (e.g. iso- and anteiso-C_17:0-branched fatty acids), except in the deepest zone. In contrast to the isotopes, variation in trace elements within the fracture zones was generally up to several orders of magnitude. Manganese and REE, as oppose to the other metals, were higher in the shallow fracture zones (112–1130 and 44–97 ppm, respectively) than in the deeper (28–272 and 5–11 ppm, respectively), in agreement with the groundwater composition. Although the rock types varied between and within the different fracture zones, this had insignificant influence on the trace element chemistry of the calcites. Co-variation was generally relatively large for many trace elements, with isometric logratio correlation generally better than 0.75, which indicates that their variation in the calcites is due to variation of Ca in the fracture water, but other local factors, especially uptake in co-precipitating minerals (clay minerals, barite, pyrite and zeolites), but also microbial activity and metal speciation may have influenced the metal incorporation into calcite. These detailed studies of fracture calcite are of importance for the understanding of variation in fluid chemistry and trace metal uptake in fracture zones, adding together with hydrochemical studies detailed information optimal for site characterisation.     

Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Calcite fracture fillings as indicators of paleohydrology at Laxemar at the Äspö Hard Rock Laboratory,southern Sweden

Isotopic compositions of C (δ¹³C), O (δ¹⁸O) and Sr (δ⁸⁷Sr) were determined for calcite fracture fillings in the crystalline rock penetrated by a 1.6 km drill hole at Laxemar, near the Äspö Hard Rock Laboratory (ÄHRL) in southern Sweden. These calcites precipitated from groundwater some time in the past, and their δ¹³C, δ¹⁸O and δ⁸⁷Sr values reflect those of the source waters. The present-day groundwater system is hydrochemically stratified with highly saline water underlying more shallow brackish and fresh water. The origin of this stratified system is probably related to past glaciations although the ultimate origin of the deep, highly saline water is still problematical. None of the calcite fracture fillings sampled below 900 m could have precipitated from any of the present-day ground waters which in view of the glacial history of the region is not surprising. However, several shallow calcite fracture fillings are formed by precipitation from the present-day groundwater. Coupled variations in δ¹³C, δ¹⁸O and δ⁸⁷Sr isotopes at depths in excess of 900 m suggest that these isotope systems in calcite are recording a time-dependent evolution of groundwater composition.     

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‰).     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.     

黔西北天桥铅锌矿床热液方解石C、O同位素和REE地球化学

利用连续流动质谱和电感耦合等离子体质谱(ICP-MS)对黔西北天桥铅锌矿床原生矿石中脉石矿物热液方解石C、O同位素组成和稀土元素含量进行了分析,结果表明热液方解石C、O同位素组成相对均一,不同标高方解石C、O同位素组成不具明显差别,其δ13CPDB和δ18OSMOW分别为-3.4‰～-5.3‰和14.7‰～19.5‰,在δ13CPDB-δ18OSMOW图上介于原始碳酸岩与海相碳酸盐岩之间。热液方解石总稀土元素含量较低(ΣREE=6.80×10-6～49.1×10-6),表现为轻稀土富集、Eu负异常的"M"型,其Eu/Eu*变化范围为0.30～0.55,与硫化物具有相似的稀土配分模式。根据热液方解石与蚀变围岩、远矿围岩及不同时代地层碳酸盐岩的C、O同位素组成和REE含量特征对比结果,结合前人研究成果,认为该矿床成矿流体具"多来源混合"特征,其中围岩碳酸盐岩为成矿流体提供了主要的C和REE来源,地层中膏岩海相硫酸盐岩为成矿流体提供了主要的S来源,而成矿流体中的水则主要为变质基底昆阳群等提供的变质水,并受到大气降水的影响。     

Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Association of Electrum and Calcite and Its Significance to the Genesis of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract. Mineral assemblage, precipitation sequence and textures of the gold‐bearing veins from the Hishikari epithermal vein‐type deposits, southern Kyushu, Japan, were examined. In addition, fluid inclusion microthermometry and carbon and oxygen isotopic compositions of calcite were determined. Calcite, and that replaced by quartz, were commonly observed throughout the precipitation sequence of the veins. Thus, calcite must be a more common gangue constituent initially than observed presently. Association of calcite and electrum is observed immediately subsequent to columnar adularia in some vein samples. In addition, close association of electrum with pseudo‐acicular quartz, and electrum with truscottite were observed. The initial coprecipitation of electrum and calcite might be a common phenomenon in the gold‐bearing veins at the Hishikari deposits. The Th (homogenization temperature) data from the Honko‐Sanjin deposits are generally higher than those from the Yamada deposit. Samples that show association of calcite and electrum yielded higher Th (206–217°C, average) than the Th data from calcite associated with low‐grade Au ore or barren (180–204°C, average). The measured Tm (temperature of last melting point of ice) range from ‐0.4 to 0.0°C. The result suggests that the salinity of the hydrothermal solution was low during the precipitation both of calcite associated with Au mineralization and of barren calcite. Fluid inclusion evidence suggestive of boiling of hydrothermal solution for the precipitation of calcite was not recognized in the present work. The δ¹³C and δ¹⁸O values of calcite range from ‐10.8 to —4.7 % and from +3.2 to +15.2 %, respectively. The δ¹³C value of H₂CO₃ and the δ¹⁸O value of H₂O in the hydrothermal fluids calculated assuming isotopic equilibrium with calcite using the temperature obtained by fluid inclusion microthermometry, range from ‐14.4 to ‐9.1 %, and from ‐6.2 to +5.5 %, respectively. Thus, the calculated δ¹⁸O values of H₂O for calcite further confirm the presence of the ¹⁸O‐enriched ore fluids during the mineralization at the Hishikari deposits. The hydrothermal solution isotopically equilibrated with the sedimentary basement rocks was responsible for the gold mineralization associated with calcite.     

Isotope systematics of secondary minerals from the Prospect Intrusion,New South Wales

The differentiated Mesozoic alkali dolerite Prospect Intrusion contains a wide range of secondary minerals, including carbonates (primarily calcite), laumontite, prehnite and heulandite, whose stability relationships imply a formation temperature of <200°C. The δ¹⁸O data for carbonates define a higher temperature (160 – 195°C) suite, and a lower temperature (51 – 73°C) suite. The δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr isotope systematics for these carbonates suggest derivation of the higher temperature group from magmatic fluids, whereas the other group had a major meteoric component that probably originated from porewater in the country rock. Source fluids for prehnite were meteoric rather than magmatic in origin based on their δD and δ¹⁸O ratios. Early in the intrusion's emplacement, CO₂-rich hydrothermal fluids formed a carbonate rind sealing the upper part of the hydrothermal system and produced the higher temperature carbonates (calcite) and laumontite. Later, cooler fluids with a meteoric component infiltrated vesicles and fractures, depositing the lower temperature carbonates (calcite, aragonite), heulandite and prehnite.     

REE, Mn, Fe, Mg and C, O Isotopic Geochemistry of Calcites from Furong Tin Deposit, South China: Evidence for the Genesis of the Hydrothermal Ore-forming Fluids

The Furong tin deposit in the central Nanling region, South China, consists of three main types of mineralization ores, i.e. skarn-, altered granite- and greisen-type ores, hosted in Carboniferous and Permian strata and Mesozoic granitic intrusions. Calcite is the dominant gangue mineral intergrown with ore bodies in the orefield. We have carried out REE, Mn, Fe, and Mg geochemical and C, and O isotopic studies on calcites to constrain the source and evolution of the ore-forming fluids. The calcites from the Furong deposit exhibit middle negative Eu anomaly (Eu/Eu*= 0.311–0.921), except for one which has an Eu/Eu* of 1.10, with the total REE content of 5.49–133 ppm. The results show that the calcites are characterized by two types of REE distribution patterns: a LREE-enriched pattern and a flat REE pattern. The LREE-enriched pattern of calcites accompanying greisen-type ore and skarn-type ore are similar to those of Qitianling granite. The REE, Mn, Fe, and Mg abundances of calcites exhibit a decreasing tendency from granite rock mass to wall rock, i.e. these abundances of calcites associated with altered granite-type and greisen-type ores are higher than those associated with skarn-type ores. The calcites from primary ores in the Furong deposit show large variation in carbon and oxygen isotopic compositions. The δ¹³C and δ¹⁸O of calcites are −0.4 to −12.7‰ and 2.8 to 16.4‰, respectively, and mainly fall within the range between mantle or magmatic carbon and marine carbonate. The calcites from greisen and altered granite ores in the Furong deposit display a negative correlation in the diagram of δ¹³C versus δ¹⁸O, probably owing to the CO₂-degassing of the ore-forming fluids. From the intrusion to wall-rock, the calcites display an increasing tendency with respect to δ¹³C values. This implies that the carbon isotopic compositions of the ore-bearing fluids have progressively changed from domination by magmatic carbon to sedimentary carbonate carbon. In combination with other geological and geochemical data, we suggest that the ore-forming fluids represent magmatic origin. We believe that the fluids exsolved from fractionation of the granitic magma, accompanying magmatism of the Qitianling granite complex, were involved in the mineralization of the Furong tin polymetallic deposit.     

Isotopic and morphological features of fracture calcite from granitic rocks of the Tono area,Japan: a promising palaeohydrogeological tool

This study aimed to develop a methodology for assessing the hydrochemical evolution of a groundwater system, using fracture-filling and fracture-lining calcite. Fracture calcite in deep (to ca. 1000 m) granitic rocks of the Tono area, central Japan, was investigated by optical and electron microscopy, and chemical and isotopic analysis. Coupled with geological evidence, these new data imply 3 main origins for the waters that precipitated calcite: (1) relatively high-temperature hydrothermal solutions, precipitating calcite distinguished by δ¹⁸O_SMOW from −3 to ca. 10‰, and with δ¹³C_PDB from ca. −18 to −7‰; (2) seawater, probably partly of Miocene age, which precipitated calcite distinguished by δ¹³C_PDB of ca. 0‰ and δ¹⁸O_SMOW > ca. 20‰; (3) fresh water, with a variable δ¹³C_PDB composition, but which precipitated calcite distinguished by δ¹³C_PDB that was significantly < 0‰ and as low as ca. −29‰ and δ¹⁸O_SMOW > ca. 17‰. Data for ¹⁴C suggest that at least some of the fresh-water calcite formed within the last 50 ka. The present day hydrogeological regime in the Tono area is also dominated by fresh groundwater. However, the marine calcite of probable Miocene age found at depth has shown no evidence for dissolution and many different calcite crystal forms have been preserved. Studies of other groundwater systems have correlated similar crystallographic variations with variations in the salinity of coexisting groundwaters. When this correlation is applied to the Tono observations, the calcite crystal forms imply a similar range of groundwater salinity to that inferred from the isotopic data. Thus, the present study suggests that even in presently low-salinity groundwater systems, calcite morphological variations may record the changing salinity of coexisting groundwaters. It is suggested that calcite morphological data, coupled with isotopic data, could provide a powerful palaeohydrogeological tool in such circumstances.     

Diagenesis and geochemistry of porites corals from Papua New Guinea: Implications for paleoclimate reconstruction

Coral proxy records of sea surface temperature (SST) and hydrological balance have become important tools in the field of tropical paleoclimatology. However, coral aragonite is subject to post-depositional diagenetic alteration in both the marine and vadose environments. To understand the impact of diagenesis on coral climate proxies, two mid-Holocene Porites corals from raised reefs on Muschu Island, Papua New Guinea, were analysed for Sr/Ca, δ¹⁸O, and δ¹³C along transects from 100% aragonite to 100% calcite. Thin-section analysis showed a characteristic vadose zone diagenetic sequence, beginning with leaching of primary aragonite and fine calcite overgrowths, transitional to calcite void filling and neomorphic, fabric selective replacement of the coral skeleton. Average calcite Sr/Ca and δ¹⁸O values were lower than those for coral aragonite, decreasing from 0.0088 to 0.0021 and −5.2 to −8.1‰, respectively. The relatively low Sr/Ca of the secondary calcite reflects the Sr/Ca of dissolving phases and the large difference between aragonite and calcite Sr/Ca partition coefficients. The decrease in δ¹⁸O of calcite relative to coral aragonite is a function of the δ¹⁸O of precipitation. Carbon-isotope ratios in secondary calcite are variable, though generally lower relative to aragonite, ranging from −2.5 to −10.4%. The variability of δ¹³C in secondary calcite reflects the amount of soil CO₂ contributing ¹³C-depleted carbon to the precipitating fluids. Diagenesis has a greater impact on Sr/Ca than on δ¹⁸O; the calcite compositions reported here convert to SST anomalies of 115°C and 14°C, respectively. Based on calcite Sr/Ca compositions in this study and in the literature, the sensitivity of coral Sr/Ca-SST to vadose-zone calcite diagenesis is 1.1 to 1.5°C per percent calcite. In contrast, the rate of change in coral δ¹⁸O-SST is relatively small (−0.2 to 0.2°C per percent calcite). We show that large shifts in δ¹⁸O, reported for mid-Holocene and Last Interglacial corals with warmer than present Sr/Ca-SSTs, cannot be caused by calcite diagenesis. Low-level calcite diagenesis can be detected through X-ray diffraction techniques, thin section analysis, and high spatial resolution sampling of the coral skeleton and thus should not impede the production of accurate coral paleoclimate reconstructions.     

Isotopic-geochemical characteristics of the lost city hydrothermal field

The isotopic (δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr/⁸⁶Sr) and geochemical characteristics of hydrothermal solutions from the Mid-Atlantic Ridge and the material of brucite-carbonate chimneys at the Lost City hydrothermal field at 30°N, MAR, were examined to assay the role of the major factors controlling the genesis of the fluid and hydrothermal chimneys of the Lost City field. The values of δD and δ¹⁸O in fluid samples indicates that solutions at the Lost City field were produced during the serpentinization of basement ultramafic rocks at temperatures higher than 200°C and at relatively low fluid/rock ratios (<1). The active role of serpentinization processes in the genesis of the Lost City fluid also follows from the results of the electron-microscopic studying of the material of hydrothermal chimneys at this field. The isotopic (δ¹⁸O, δ¹³C, and ⁸⁷Sr/⁸⁶Sr) and geochemical (Sr/Ca and REE) signatures indicate that, before its submarine discharging at the Lost City field, the fluid filtered through already cold altered outer zones of the Atlantis Massif and cooled via conductive heat loss. During this stage, the fluid could partly dissolve previously deposited carbonates in veins cutting serpentinite at the upper levels of the Atlantis Massif and the carbonate cement of sedimentary breccias underlying the hydrothermal chimneys. Because of this, the age of modern hydrothermal activity at the Lost City field can be much younger than 25 ka.     

Isotopic geochemistry of burial-metamorphosed volcanogenic sediments,Great Valley sequence,northern California

Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ¹⁸O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ¹⁸O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ¹⁸O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ¹⁸O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ¹³C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCO^t-₃ was continuously enriched in ¹³C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ¹⁸O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.     

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.     

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee,Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ¹⁸O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in ¹⁸O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO₃²⁻] (∼50 μmol/l) in the surface waters. The resulting weighted average δ¹⁸O value for the studied period is −9.6‰, compared with a calculated equilibrium δ¹⁸O value of −9.4‰. These data convincingly demonstrate that δ¹⁸O of calcite are, for the most part, a very reliable proxy for temperature and δ¹⁸O of the water.     

Nature of the Ore-Forming Fluid at the Quaternary Noya Gold Deposit in Kyushu,Japan

We discuss the nature of the ore-forming hydrothermal fluid in the Noya gold-bearing calcite-quartz-adularia veins of central Kyushu, Japan on the basis of oxygen, carbon, and strontium isotope ratios, and aqueous speciation calculations for the present-day geothermal fluid. The isotopic values of the Noya ore-forming fluid were estimated to be −6.5‰ for δ¹³C and −7.5‰ for δ¹⁸O. The oxygen isotopic equilibrium temperatures for vein calcite are more than 180°C at the bottom of the Noya mineralization zone, and decrease with increasing elevation. As the temperature decreased, the dominant carbon species in the fluid changed from H₂CO₃ to HCO₃^- at about 120°C. The equilibrium temperatures for vein quartz are consistent with the calcite calculations. The carbon and oxygen isotope trends of the Noya vein calcite and the isotope ratios of strontium suggest that the fluids that precipitated the Noya veins were controlled by an andesite-dominated geology. Chondrite-normalized REE patterns for the white-colored veins from wells 51-WT-1 and 51-WT-2 displayed a light REE-rich pattern with positive Eu anomalies, suggesting the existence of a reducing environment for the fluid. The pyrite-rich gray-colored veins and a silicified rock from well 51-WT-2 showed higher REE concentrations than did the white veins. Altered host andesitic rocks have similar REE patterns to that of the silicified rock, and have higher REE contents than the others in the drill cores. Aqueous speciation calculations showed that the fluid in the hydrothermal reservoir is currently in muscovite stability. The fluid at the ore-mineralization stage may have contained more potassium or have had a higher pH, so that adularia precipitated with calcite and quartz, as well as gold. Fluid boiling at depth in the system produced the gold-bearing calcite-quartz-adularia veins.     

Sedimentological and palaeohydrological responses to tectonics and climate in a small, closed, lacustrine system: Oligocene As Pontes Basin (Spain)

ABSTRACT A small, closed, lacustrine system developed during the restraining overstep stages of the Oligocene As Pontes strike‐slip basin (Spain). The increase in basin accommodation and the headward spread of the drainage, which increased the water input, triggered a change from shallow, holomictic to deeper, meromictic conditions. The lower, shallow, lacustrine assemblage consists of mudstone–carbonate cycles recording lacustrine–palustrine ramp deposition in a saline lake. High Sr content in some early diagenetic calcites suggests that aragonite and calcite made up the primary carbonate muds. Early dolomitization took place together with widespread pedogenic activity. The upper, deep, freshwater, lacustrine assemblage includes bundles of carbonate–clay rhythmites and fine‐grained turbidite beds. Primary calcite and diagenetic siderite make up the carbonate laminae. The Mg content of the primary carbonates records variations in Mg/Ca ratios in lacustrine waters. δ¹⁸O and δ¹³C covariance trends in calcite reinforce closed drainage conditions. δ¹⁸O data indicate that the lake system changed rapidly from short‐lived isotopically light periods (i.e. from seasonal to pluriannual) to longer steady‐state periods of heavier δ¹⁸O (i.e. from pluriannual to millennial). The small δ¹³C changes in the covariant trends were caused by dilute inflow, changing the contributions of dissolved organic carbon in the system and/or internal variations in lacustrine organic productivity and recycling. In both shallow and deep carbonate facies, sulphate reduction and methanogenesis may account, respectively, for the larger negative and positive δ¹³C shifts recorded in the early diagenetic carbonates (calcite, dolomite and siderite). The lacustrine system was very susceptible to high‐frequency, climatically forced water balance variations. These climatic oscillations interfered with the low‐frequency tectonic and morphological changes in the basin catchment. This resulted in the superposition of high‐order depositional, mineralogical and geochemical cycles and rhythms on the lower order lacustrine infill sequence.     

Diagenesis of Pennsylvanian phylloid algal mounds from the southern Cantabrian Zone (Spain)

The Pennsylvanian phylloid algal mounds exposed in the Cervatina Limestone of the Cantabrian Zone (NW Spain) developed during the highstands of high-frequency shallowing-upward cycles and lack evidence of subaerial exposure at their tops. Mound core facies are composed of massive bafflestones with variable amounts of calcite cements and anchicodiacean phylloid algae with cyathiform thalli preserved in growth position. Through standard petrographic, isotopic (δ¹⁸O and δ¹³C), major and trace element (Ca, Mg, Fe, Mn, Sr) and cathodoluminescence analyses, five calcite cement phases (cement 1 (C1)–cement 5 (C5)) have been identified filling primary and secondary pores. Early marine diagenesis is represented by micritization and non-luminescent to mottled-dull luminescent high-Mg calcite fibrous marine cement (C1). A dissolution phase then occurred and created vuggy and moldic pores. Based on the absence of field or petrographical or geochemical evidence of exposure, it is inferred that dissolution occurred in near-surface undersaturated marine waters with respect to aragonite related to progressive organic matter oxidation. Secondary porosity was subsequently filled by dull-bright-dull bladed high-Mg calcite (C2), which precipitated in the early shallow burial from marine-derived pore waters. Remaining porosity was occluded by shallow-burial precipitates consisting of non-luminescent scalenohedral low-Mg calcite (C3) followed by non-ferroan dull luminescent calcite spar (C4). Latter phases of calcite spar exhibiting non- and dull luminescence (C5) are associated with burial calcite veins. Low δ¹⁸O values (around ?8‰), moderately depleted δ¹³C values (around 0.5‰) and the homogeneity of trace element contents of carbonate matrix, cements and vein-filling calcites suggest burial isotopic re-equilibration and recrystallization, probably in Early Permian times during post-thrusting orocline formation.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.