Petrography and geochemistry of early-stage, fine- and medium-crystalline dolomites in the Middle Devonian Presqu'ile Barrier at Pine Point, Canada

The petrography and geochemistry of fine- and medium-crystalline dolomites of the Middle Devonian Presqu’ile barrier at Pine Point (Western Canada Sedimentary Basin) are different from those of previously published coarse-crystalline and saddle dolomites that are associated with late-stage hydrothermal fluids. Fine-crystalline dolomite consists of subhedral to euhedral crystals, ranging from 5 to 25 μm (mean 8 μm). The dolomite interbedded with evaporitic anhydrites that occur in the back-barrier facies in the Elk Point Basin. Fine-crystalline dolomite has δ¹⁸Ο values between ?1·6 to –3·8‰ PDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7079–0·7081, consistent with derivation from Middle Devonian seawater. Its Sr concentrations (55–225 p.p.m., mean 105 p.p.m.) follow a similar trend to modern Little Bahama seawater dolomites. Its rare earth element (REE) patterns are similar to those of the limestone precursors. These data suggest that this fine-crystalline dolomite formed from Middle Devonian seawater at or just below the sea floor. Medium-crystalline dolomite in the Presqu’ile barrier is composed of anhedral to subhedral crystals (150–250 μm, mean 200 μm), some of which have clear rims toward the pore centres. This dolomite occurs mostly in the southern lower part of the barrier. Medium-crystalline dolomite has δ¹⁸O values between ?3·7 to ?9·4‰ PDB (mean ?5·9‰ PDB) and ⁸⁷Sr/⁸⁶Sr ratios from 0·7081–0·7087 (mean 0·7084); Sr concentrations from 30 to 79 p.p.m. (mean 50 p.p.m.) and Mn content from 50 to 253 p.p.m. (mean 161 p.p.m.); and negative Ce anomalies compared with those of marine limestones. The medium-crystalline dolomite may have formed either (1) during shallow burial at slightly elevated temperatures (35–40 °C) from fluids derived from burial compaction, or, more likely (2) soon after deposition of the precursor sediments by Middle Devonian seawater derived from the Elk Point Basin. These results indicate that dolomitization in the Middle Devonian Presqu’ile barrier occurred in at least two stages during evolution of the Western Canada Sedimentary Basin. The geochemistry of earlier formed dolomites may have been modified if the earlier formed dolomites were porous and permeable and water/rock ratios were large during neomorphism.     

Constraints of Sr isotopic compositions of apatite and carbonates on the origin of Fe and Cu mineralizing fluids in the Lala Fe-Cu-(Mo,LREE) deposit,SW China

Numerous Fe-Cu deposits with mineralization styles similar to iron oxide-copper gold (IOCG) deposits form the Kangdian Fe-Cu metallogenic province, southwestern (SW) China. As one of the largest deposits in the region, the ~ 1.0 Ga Lala Fe-Cu deposit is hosted in a Paleoproterozoic volcanic-sedimentary succession named the Hekou Group which is alternately intruded by ~ 1.0 Ga doleritic plutons. This deposit has a paragenetic sequence evolving from Stage I of Na-alteration to Stage II of Fe mineralization, and finally to Stage III of Cu-(Mo, REE) mineralization, coeval with mafic-felsic intra-plate magmatism in the region. This study conducted in-situ Sr isotopic analyses on apatite and carbonate, aiming to resolve the long controversial issue regarding the origin of the Fe and Cu mineralizing fluids in the deposit. Apatite of Stage II has ⁸⁷Sr/⁸⁶Sr ratios varying from 0.71380 to 0.72733, much higher than those of synchronous igneous rocks in the region (0.7074 to 0.7091), but similar to the Paleoproterozoic host rocks (0.71368 to 0.71837 at ~ 1.0 Ga). This similarity indicates that radiogenic Sr of the Fe mineralizing fluid was dominantly sourced from the host rocks. Apatite and calcites of Stage III have ⁸⁷Sr/⁸⁶Sr ratios (0.75758–0.79293) much higher than apatite of Stage II and the host rocks but similar to the Archean basement rocks (as high as 0.80 at ~ 1.0 Ga) beneath the cover of the Yangtze Block, suggesting that the highly radiogenic Sr isotopic composition of the Cu mineralizing fluid was mainly inherited from the old basement rocks. In combination with previous C-O-S isotopic data indicating a magma-hydrothermal origin, it was suggested that the Fe mineralizing fluid was exsolved from a mafic magma that generated the ~ 1.0 Ga doleritic plutons, and inherited radiogenic Sr from the host rocks during fluid-rock interaction. By contrast, the Cu mineralizing fluid might have been sourced from another pulse of magmatic, Cu-Mo-REE- and CO₂-rich fluid which have once interacted with Archean basement rocks prior to mineralization. The source of such a Cu-Mo-REE-rich fluid was not well constrained in current study but was inferred to be exsolved from a hidden felsic magma. We propose that intrusions of the bimodal magmas in Kangdian are responsible for regional hydrothermal circulation which led to Fe-Cu-(Mo, REE) mineralization in the Kangdian province.     

Geochemical constraints on the origin of the Kicking Horse and Monarch Mississippi Valley-type lead-zinc ore deposits, southeast British Columbia, Canada

Two Mississippi Valley-type (MVT) ore deposits, Kicking Horse and Monarch, have been studied with the aim of comparing the ores at the two localities and to characterize the origin of the mineralizing fluids and the ore formation process(es). Both deposits are hosted by the Middle Cambrian Cathedral Formation carbonate host rocks, Kicking Horse on the north and Monarch on the south flank of the Kicking Horse valley near Field (SE British Columbia). The ore bodies are situated at the transition of (western) basinal to (eastern) shallow-water strata of the paleo-Pacific passive margin succession in the Cordilleran Foreland Province of the Western Canada Sedimentary Basin. Both deposits are related spatially to normal faults. In both localities, the ore minerals are dominated by pyrite, sphalerite, and galena. Dolomite, minor quartz, and calcite are also present in close association with the ores. The salinity (21–30 wt% NaCl eq.) and homogenization temperatures (63–182°C) measured in fluid inclusions in carbonate, quartz, and sphalerite lie within the typical range of MVT fluid conditions. The good stoichiometry (50–53 mol% CaCO₃), low δ¹⁸O values (−21 to −14‰ Vienna Peedee belemnite) and relatively high homogenization temperatures (>95°C) of the dolomite suggest the dolomites were formed under burial diagenesis. The ore-forming fluids probably interacted with siliciclastic units, based on elevated Li contents and ⁸⁷Sr/⁸⁶Sr ratios, which are highest in the dolomite type after the main ore stage. We propose that the ores formed from the mixing of a downward-infiltrating, sulfur-bearing halite-dissolution fluid with an upward-migrating, metal-rich evaporated seawater fluid, which had already undergone minor mixing with a dilute fluid.     

Numerical modeling of hydrothermal fluid flow coupled with mass transport: An example from the Devonian Wabamun Group, northeast British Columbia, Canada

Several researchers have suggested that upward and lateral hydrothermal fluid flow was responsible for dolomitization of various Devonian and Mississippian reservoirs in the Western Canada Sedimentary Basin (WCSB) based on sedimentological, geochemical and diagenetic evidence. In this study, a numerical model was applied to investigate hydrothermal fluid flow in the Wabamun Group, Parkland field, northeastern British Columbia, Canada. Our numerical results indicate that faults play the most critical role in controlling hydrothermal fluid flow. They provide a pathway connecting the basement of the basin and overlying sedimentary layers. Upwelling fluid flow via faults may bring reactants and heat from underlying strata to shallow formations for diagenetic reactions (e.g. dolomitization and/or chertification) or forming ore deposits. Salinity distribution of formation water, permeability configuration of host rock and regional fluid flow are also important factors affecting hot and brine fluid flow and accompanying heat and mass distribution.     

Sr, C and O isotope systematics in the Pucará basin, central Peru

A combined Sr, O and C isotope study has been carried out in the Pucará basin, central Peru, to compare local isotopic trends of the San Vicente and Shalipayco Zn-Pb Mississippi Valley-type (MVT) deposits with regional geochemical patterns of the sedimentary host basin. Gypsum, limestone and regional replacement dolomite yield ⁸⁷Sr/⁸⁶Sr ratios that fall within or slightly below the published range of seawater ⁸⁷Sr/⁸⁶Sr values for the Lower Jurassic and the Upper Triassic. Our data indicate that the Sr isotopic composition of seawater between the Hettangian and the Toarcian may extend to lower ⁸⁷Sr/⁸⁶Sr ratios than previously published values. An ⁸⁷Sr-enrichment is noted in (1) carbonate rocks from the lowermost part of the Pucará basin, and (2) different carbonate generations at the MVT deposits. This indicates that host rocks at MVT deposits and in the lower-most part of the carbonate sequence interacted with ⁸⁷Srenriched fluids. The fluids acquired their radiogenic nature by interaction with lithologies underlying the carbonate rocks of the Pucará basin. The San Ramón granite, similar Permo-Triassic intrusions and their clastic derivatives in the Mitu Group are likely sources of radiogenic ⁸⁷Sr. The Brazilian shield and its erosion products are an additional potential source of radiogenic ⁸⁷Sr. Volcanic rocks of the Mitu Group are not a significant source for radiogenic ⁸⁷Sr; however, molasse-type sedimentary rocks and volcaniclastic rocks cannot be ruled out as a possible source of radiogenic ⁸⁷Sr. The marked enrichment in ⁸⁷Sr of carbonates toward the lower part of the Pucará Group is accompanied by only a slight decrease in ¹⁸O values and essentially no change in ¹³C values, whereas replacement dolomite and sparry carbonates at the MVT deposits display a coherent trend of progressive ⁸⁷Sr-enrichment, and ¹⁸O- and ¹³C-depletion. The depletion in ¹⁸O in carbonates from the MVT deposits are likely related to a temperature increase, possibly coupled with a ¹⁸O-enrichment of the ore-forming fluids. Progressively lower ¹³C values throughout the paragenetic sequence at the MVT deposits are interpreted as a gradually more important contribution from organically derived carbon. Quantitative calculations show that a single fluid-rock interaction model satisfactorily reproduces the marked ⁸⁷Sr-enrichment and the slight decrease in ¹⁸O values in carbonate rocks from the lower part of the Pucará Group. By contrast, the isotopic covariation trends of the MVT deposits are better reproduced by a model combining fluid mixing and fluid-rock interaction. The modelled ore-bearing fluids have a range of compositions between a hot, saline, radiogenic brine that had interacted with lithologies underlying the Pucará sequence and cooler, dilute brines possibly representing local fluids within the Pucará sequence. The composition of the local fluids varies according to the nature of the lithologies present in the neighborhood of the different MVT deposits. The proportion of the radiogenic fluid in the modelled fluid mixtures interacting with the carbonate host rocks at the MVT deposits decreases as one moves up in the stratigraphic sequence of the Pucará Group.     

Role of basement in epithermal deposits: The Kushikino and Hishikari gold deposits,southwestern Japan

The magma–ore deposit relationship of most low-sulfidation epithermal ore deposits is still unclear, partly because many stable isotopic studies of such deposits have indicated the predominance of meteoric waters within hydrothermal fluids. However, it is certainly true that hydrothermal systems are ultimately driven by magmatic intrusions, and epithermal gold deposits might therefore be produced by magmatic activity even in deposits having has no obvious links to a magma. We re-examine the genesis of two typical low-sulfidation epithermal gold deposits, the Kushikino and Hishikari deposits, using structural simulations and isotope data.Many epithermal gold deposits including the Kushikino and Hishikari deposits have been discovered in Kyushu, southwestern Japan. The Kushikino deposit comprises fissure-filling veins within Neogene andesitic volcanics that overlie unconformably Cretaceous sedimentary basement. The veins consist of gold- and silver-bearing quartz and calcite with minor amounts of adularia, sericite and sulfides. Although carbon and oxygen isotopic data for the veins indicate a meteoric origin of the ore fluid, finite element simulations suggest that the vein system might have formed in direct response to magma intrusion. In particular, geophysical data suggest that intruding magma has uplifted the basement rocks, thereby producing fractures and veins and a positive Bouguer anomaly, and providing the heat necessary to drive an ore-forming hydrothermal system.The second component of this study has been to investigate the nature and evolution of the Kushikino and Hishikari epithermal systems. Isotope data document the geochemical evolution of the hydrothermal fluids. We conclude that the existence of sedimentary basement rocks at depth might have affected the strontium and carbon isotopic ratios of the Kushikino and Hishikari ore fluids. The ⁸⁷Sr/⁸⁶Sr ratios and δ¹³C–δ¹⁸O trend reveal that major ore veins in the Hishikari deposit can be distinguished from shallow barren veins. It was suggested isotopically that fluids responsible for the barren veins in nearby shallow and barren circulation systems were only controlled by the shallow host rocks. Such multi-isotope systematics provide a powerful tool with which to determine the center of hydrothermal activity and thereby document the evolution of hydrothermal fluids.     

Role of basement in epithermal deposits: The Kushikino and Hishikari gold deposits, southwestern Japan

The magma–ore deposit relationship of most low-sulfidation epithermal ore deposits is still unclear, partly because many stable isotopic studies of such deposits have indicated the predominance of meteoric waters within hydrothermal fluids. However, it is certainly true that hydrothermal systems are ultimately driven by magmatic intrusions, and epithermal gold deposits might therefore be produced by magmatic activity even in deposits having has no obvious links to a magma. We re-examine the genesis of two typical low-sulfidation epithermal gold deposits, the Kushikino and Hishikari deposits, using structural simulations and isotope data.Many epithermal gold deposits including the Kushikino and Hishikari deposits have been discovered in Kyushu, southwestern Japan. The Kushikino deposit comprises fissure-filling veins within Neogene andesitic volcanics that overlie unconformably Cretaceous sedimentary basement. The veins consist of gold- and silver-bearing quartz and calcite with minor amounts of adularia, sericite and sulfides. Although carbon and oxygen isotopic data for the veins indicate a meteoric origin of the ore fluid, finite element simulations suggest that the vein system might have formed in direct response to magma intrusion. In particular, geophysical data suggest that intruding magma has uplifted the basement rocks, thereby producing fractures and veins and a positive Bouguer anomaly, and providing the heat necessary to drive an ore-forming hydrothermal system.The second component of this study has been to investigate the nature and evolution of the Kushikino and Hishikari epithermal systems. Isotope data document the geochemical evolution of the hydrothermal fluids. We conclude that the existence of sedimentary basement rocks at depth might have affected the strontium and carbon isotopic ratios of the Kushikino and Hishikari ore fluids. The ⁸⁷Sr/⁸⁶Sr ratios and δ¹³C–δ¹⁸O trend reveal that major ore veins in the Hishikari deposit can be distinguished from shallow barren veins. It was suggested isotopically that fluids responsible for the barren veins in nearby shallow and barren circulation systems were only controlled by the shallow host rocks. Such multi-isotope systematics provide a powerful tool with which to determine the center of hydrothermal activity and thereby document the evolution of hydrothermal fluids.     

Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Strontium Isotopic Signatures of the Streams and Lakes of Taylor Valley, Southern Victoria Land, Antarctica: Chemical Weathering in a Polar Climate

We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different ⁸⁷Sr/⁸⁶Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system could be either the Cenozoic volcanic rocks that make up a small portion of the till deposited in the valley during the Last Glacial Maximum or from marble derived from the local basement rocks. The more radiogenic ratios from Lake Bonney originate from ancient salt deposits that flow into the lake from Taylor Glacier and the weathering of minerals with more radiogenic Sr isotopic ratios within the tills. The Sr isotopic data from the streams and lakes of Taylor Valley strongly support the notion documented by previous investigators that chemical weathering has been, and is currently, a major process in determining the overall aquatic chemistry of these lakes in this polar desert environment.     

Isotopic Geochemistry of Chinese Fluorite Deposits

China is one of the richest countries in the world in terms of fluorite resources. On the basis of host rocks and mineralization patterns, the fluorite deposits in China have been classified into three types: (1) those occurring in Mesozoic volcanic regions, mainly consisting of veinfilling deposits of the quartz-fluorite association (Type I); (2) those occurring in granite areas, chiefly belonging to veinfilling deposits of the quartz-fluorite association or veinfilling or altered-rock deposits associated with Pb, Zn, W, Sn, etc. (Type II); and (3) those occurring in carbonate rocks as bedded deposits of quartz-fluorite, sulfide-fluorite, and quartz-barite-calcite-fluorite assemblages (Type III).

This paper summarizes the characteristics of fluorite deposits in China on the basis of strontium-, hydrogen-, and oxygen-isotopic and geochronological data, as well as geological investigations of deposits from 22 mining districts. δ¹⁸O and δD values of ore-forming fluids are ?10.2 to +3.7‰ and ?77.9 to 41.0‰, respectively, for Type-I deposits, ?13.1 to ?4.9‰ and ?65.5 to ?41.7‰ for Type-II deposits, and -5.6 to +4.3‰ and ?80 to ?29‰ for Type-Ill deposits. Study of the isotopic water-rock exchange indicates that the mineralizing fluids for these types of deposits have been derived mostly from circulating geothermal water that originated from Mesozoic meteoric water. The differences in the isotopic characteristics of hydrothermal systems for various types of deposits depend mainly on isotopic exchange between water and rocks, the water/rock values being 0.05 to 2.0 for Type-I deposits, generally more than 2.0 for Type-II deposits, and 0.5 to 3.0 for Type-Ill deposits.

The ore-forming ages for Type-I and Type-II deposits are roughly separated into three groups—230 to 180 Ma, 120 Ma, and 90 to 60 Ma. These ages successively decrease from northwestern China to southeastern coastal areas.

⁸⁷Sr/⁸⁶Sr values of 0.7306 to 0.7710 (mean 0.7513) from fluorite in the early stage (main mineralization) for Type-I deposits are higher than those from host rocks (0.7081 to 0.7260) during the mineralizing event, and mostly fall in the range of ⁸⁷Sr/⁸⁶Sr values from basement metamorphic rocks (from 0.7455 to 0.9094) during the epoch of mineralization. But the ⁸⁷Sr/⁸⁶Sr values of 0.7102 to 0.7137 (mean 0.7122) for late-stage fluorite and calcite are similar to those of surrounding host rocks. This indicates that the mineralizing materials of early stages in the formation of deposits (Type-I) originated mostly from Precambrian basement metamorphic rocks; those of later stages (Type II) were derived chiefly from host rocks. Type-II and Type-Ill deposits from different mining areas exhibit great variations in ⁸⁷Sr/⁸⁶Sr values, but are quite similar to their host rocks, indicating that the mineralizing materials in Type-II and Type-Ill deposits were derived chiefly from their host rocks.     

Rare earth element, 87Sr/86Sr,and 143Nd/144Nd compositions of Cenozoic orogenic dacites from Baja California,northwestern Mexico,and adjacent west Texas: evidence for the predominance of a subcrustal component

Dacitic lavas and ignimbrites were examined from seven localities that span the entire 700 km width of the mid- to late Cenozoic magmatic arc of northwestern Mexico and adjacent west Texas. These rocks have remarkably similar REE patterns that are parallel in the heavy REE and have modest negative Eu anomalies. Samples from three localities including Baja California, the Sierra Madre Occidental, and the Chihuahuan Basin and Range have initial ⁸⁷Sr/⁸⁶Sr between 0.7044 and 0.7050 and _Nd near 0.0±1.0. These dacites are isotopically similar to associated basalts, and they show no systematic isotopic variation that is correlated with age or composition of the basement. There is no evidence that magmas parental to these dacites interacted significantly with continental crust. Samples form three other localites in the Basin and Range vary in initial ⁸⁷Sr/⁸⁶Sr from 0.7051 to 0.7070 and _Nd from about -1 to –2. The composition of these rocks reflects contamination of the parental magmas by relatively small amounts of Precambrian crust. Collectively, the dacites of this study show much less isotopic variation than do Mesozoic granitoids (Farmer and DePaolo 1983) and late Cenozoic olivine tholeiites (Hart 1985) from similar transects of the western United States. The distinctive source region for the magmas parental to the Mexican dacites was relatively uniform isotopically, but it was enriched in LIL and HFS elements beneath the eastern Basin and Range.     

Sr and Nd Isotopic Characteristics and Magma Genesis of Mesozoic Volcanic Rocks Along the Coastal Region of Southeastern China

The Mesozoic volcanic rocks in the coastal region of southeastern China were superimposed on some different basement tectonic elements. The volcanic rocks developed in these different basement tectonic elements have great differences in Sr and Nd isotopic compositions. The rocks in western Zhejiang and northeastern Jiangxi Provinces which belong to the Lower Yangtze subplate have lower initial 87Sr/ 86Sr ratios, but are higher in initial Nd isotopic ratios. The initial 143Nd / 144Nd values of the volcanic rocks developed in the Cathaysian subplate increase clearly from early to late in time, and from the core of the Wuyishan uplift coastwards constantly, but the initial 87Sr/86Sr values tend to decrease. The isotopic characteristics and their spatial variations in Mesozoic volcanic rocks in the study region are, to a great extent, manifestations of the isotopic characteristics in basement metamorphic complexes, and the generation of the Mesozoic acid magma in this region is attributed to the recycling o     

Nd,Sr and Pb isotopic and REE geochemical study of some Miocene submarine hydrothermal deposits (Kuroko deposits) in Japan

Neodymium, Sr and Pb isotopic compositions, along with rare earth element (REE) concentrations were determined for twelve black ores and one yellow ore from twelve localities of the Kuroko deposits, Japan. The ores were generated by submarine hydrothermal activity during the Miocene age. Neodymium isotopic compositions of the ores (_Nd: –4.9 to +6.5) mostly overlap with spatially associated igneous rocks. On a Nd versus Sr isotopic correlation diagram, however, ⁸⁷Sr/⁸⁶Sr ratios are shifted from the associated igneous rocks towards the higher contemporaneous seawater ratio. REE patterns are highly variable, ranging from light REE enriched to depleted, and show no Ce anomalies, as would be expected if they were derived from seawater. These results suggest that the REEs contained in ores were mainly derived from the associated igneous rocks, but that the ore Sr is a mixture derived from both seawater and the igneous rocks. Most Pb isotopic compositions fall within the range defined by the associated igneous rocks (²⁰⁶Pb/²⁰⁴Pb=18.35–18.84, ²⁰⁷Pb/²⁰⁴Pb=15.59–15.97 and ²⁰⁸Pb/²⁰⁴Pb=38.53–39.90), although several samples have very radiogenic compositions that were most likely derived from basement rocks. Our new Pb isotopic results display greater variation, and have a larger range of more radiogenic compositions than has been noted previously for these ores. In addition, the black ore with the most radiogenic Pb isotopic composition also has the least radiogenic Nd isotopic composition. This suggests that at least some of the Pb contained in the ores was derived mainly from older basement rocks. The large positive Eu anomalies for some black ores are consistent with a high-temperature origin for the parental fluids, irrespective of the source rock. The single yellow ore examined, however, has a small negative Eu anomaly, which may indicate derivation from a lower temperature fluid. Previous studies suggested that the Kuroko ores were formed in the presence of organic materials in an anoxic basin. Combined Nd, Sr, Pb and Os isotopic and REE abundance data indicate that multiple sources were involved in the genesis of Kuroko ores.     

安徽沙坪沟斑岩钼矿床赋矿岩体钾质交代作用及其微量元素和Sr-Nd同位素响应

以沙坪沟钼矿主要的赋矿岩石——石英正长岩和花岗斑岩为对象,通过对比不同蚀变强度岩石的岩相学、岩石地球化学和同位素特征,研究该矿床的钾质交代作用-矿化特征,探讨不同热液蚀变的元素组合、蚀变过程中的元素迁移和Sr-Nd同位素的变化及其成因、不同蚀变的物理化学条件差异及其与矿化的关系,进而揭示蚀变-成矿热液流体的特征和起源。研究表明,石英正长岩和花岗斑岩的地球化学特征总体相似,显示其属同源岩浆演化产物,二者均受到钾质蚀变,但蚀变强度相差较大。钾质蚀变岩石的化学成分表现为高K_2O、Rb和低Na_2O、CaO、Sr、Ba,不同蚀变强度的岩石Rb/Sr和Sr同位素组成差别较大,花岗斑岩样品数据更显离散,甚至出现异常低的锶同位素初始值,表明热液蚀变强烈改造了Rb-Sr同位素体系,而Sm-Nd体系基本保持稳定。这一现象在东秦岭-大别钼矿带中典型的斑岩钼矿床也有出现,显示该成矿带具有相似的蚀变类型、热液起源和演化特征。而且钾长石化后期至黄铁云(绢)英岩化阶段也是最主要的钼成矿期,表明这期间流体系统pH值的降低致使Mo元素从流体中沉淀成矿。对比斑岩铜、铜-钼矿床和钼矿床的蚀变特征及其过程中元素和同位素的变化可以发现,这3种矿床均发育碱质交代作用,但蚀变强度、热液的Rb-Sr分异程度及其对原岩的改造程度存在较大差异,这暗示了各自特有的成岩、成矿物质和流体来源及大地构造背景。     

Pb and Sr isotopes in volcanic rocks from the Aleutian Islands and Pribilof Islands,Alaska

The Pb and Sr isotope ratios of Plio-Pleistocene volcanic rocks from the Aleutian volcanic arc are used as tracers of the lithospheric subduction process at the converging Pacific and Bering plates. Aleutian arc lavas do not have the same Pb isotopic compositions as volcanic rocks of the subducted Pacific ocean crust or the nearby Pribilof Islands, but appear to contain an ‘old continental crustal component’ with high ²⁰⁷Pb/²⁰⁴Pb ratio, as has been found in some other volcanic arcs.⁸⁷Sr/⁸⁶Sr ratios in the Aleutian volcanic arc rocks average 0.70322, slightly higher than fresh volcanic rocks from normal ridge segments, but within the range of values from ‘Icelandic’ ridge segments, oceanic islands and the Pribolof Islands. The Pb and Sr isotopic compositions of Aleutian lavas show a positive correlation and the range of values does not change for volcanoes distributed along strike in the arc, even though the crustal type in the hanging wall of the Benioff zone changes from oceanic in the west to continental in the east. Since the basement of the continental arc segment is older than the basement of the oceanic segment, and probably has a different isotopic character, the constancy of isotopic ratios along the arc argues against contamination by wall rocks of the type exposed in the arc.A sufficient explanation for the isotopic data is the mixture of several per cent of continent-derived sediment with melt derived from the underthrust oceanic crust and overlying mantle. This small amount of contaminant is difficult to document by geophysical observations. Such a model implies extensive recycling of Ba, Pb, K and Rb through volcanism at convergent plate margins like the Aleutians.     

Chemical and Isotopic Constraints for Recrystallization of Sedimentary Dolomites from the Western Canada Sedimentary Basin

Mississippian shoal carbonates of Western CanadaSedimentary Basin are important hydrocarbon hosts.Dolomitization plays a major role in the evolution ofreservoir porosity in these carbonates. This processvaries across the basin and reflects, in part, divergentsources and chemistry of pore fluids. Dolomites fromseveral petroleum reservoirs were analyzed formineralogical, geochemical and isotopic variation. Thedata clearly demonstrate the progressive and complexrecrystallization of dolomite during shallow and deepburial in modified marine, meteoric and burial fluids.These data include: change in crystal size,stoichiometry, cathodoluminscence characteristics,stable oxygen and carbon isotopic shifts and changesin radiogenic Sr isotopic composition. However,regional geology, tectonic history and fluid flowevolution play important roles in the diageneticimprints and the degree of recrystallization.Early microcrystalline dolomite formed in normalmarine and evaporative conditions in Mississippiancarbonates from Western Canada Sedimentary Basinhave undergone variable degrees of recrystallization, frompristine dolomite akin to Holocene sabkha dolomitewith preserved mineralogical and chemical attributesto highly recrystallized mesodolomite, however stillnonstoichiometric, but with highly altered chemicalsignatures. Careful attention should be made to localgeology, hydrodynamics and fluid flow when investigatingdolomite recrystallization in sedimentary basins.     

The influence of enclosing rock type on barite deposits, eastern Pyrenees, Spain: fluid inclusion and isotope (Sr, S, O, C) data

The Rocabruna and Coll de Pal barite deposits, located in the eastern Pyrenees of Spain, fill karstic cavities within carbonate rocks of Cambrian and Devonian age, respectively. The deposits contain barite, chalcopyrite, tetrahedrite, pyrite and minor sphalerite and galena with saddle dolomite and quartz as gangue. Fluid inclusion data from Coll de Pal quartz and dolomite indicate that the mineralizing fluid was a polysaline CaCl₂-rich brine, with temperatures between 125 and 150 °C. C and O isotopic compositions of carbonates in both deposits are consistent with a progressive increase in temperature during deposition. The ³⁴S values of barite, which range from 14.2 to 15.9‰ in Coll de Pal, and from 13.9 to 19.3‰ in Rocabruna, together with ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7118 to 0.7168 in Rocabruna, and from 0.7115 to 0.7136 in Coll de Pal, indicate two different fluid sources. We propose that these deposits formed as a result of mixing between a Ba-rich, sulfate-poor hot fluid, and sulfate-rich solutions of surficial origin. The different Sr isotope ratios in the deposits indicate that the hot Ba-rich fluids involved in each deposit were equilibrated with different rock types (carbonates and shales), in agreement with the geology of the two areas. Received: 22 October 1997 / Accepted: 24 March 1998     

Strontium and Lead Isotopic Study of the Carbonate‐hosted Xujiashan Antimony Deposit from Hubei Province,South China: Implications for its Origin

The Xujiashan antimony deposit is hosted by marine carbonates of the Upper Sinian Doushantuo and Dengying Formations in Hubei Province, South China. Our Sr isotopic data from pre‐ and syn‐mineralization calcites that host the mineralization show that the pre‐mineralization calcite displays a narrow range of ⁸⁷Sr/⁸⁶Sr ratios (0.7096 to 0.7097), similar to the ratios of the Sinian seawater, and high Sr concentrations (2645 to 8174 ppm). In contrast, the syn‐mineralization calcite exhibits low Sr concentrations (785 to 2563 ppm) and high ⁸⁷Sr/⁸⁶Sr ratios (0.7109 to 0.7154), which is interpreted as the result of addition of radiogenic strontium during the antimony mineralization. The study of Sr isotopes suggests that their Sr component to the pre‐mineralization calcite derived directly from the host rocks (i.e. the Sinian marine carbonates), while radiogenic ⁸⁷Sr for the syn‐mineralization calcite derived from the underlying Mesoproterozoic Lengjiaxi Group basement through hydrothermal fluid circulation along the major fault that hosts the mineralization. The Pb isotopic ratios of stibnite are subdivided into two groups (Group A and Group B), Group A is characterized by higher radiogenic lead, with ²⁰⁶Pb/²⁰⁴Pb = 18.874 to 19.288, ²⁰⁷Pb/²⁰⁴Pb = 15.708 to 15.805, and ²⁰⁸Pb/²⁰⁴Pb = 38.642 to 39.001. Group B shows lower lead isotope ratios (²⁰⁶Pb/²⁰⁴Pb = 17.882 to 18.171, ²⁰⁷Pb/²⁰⁴Pb = 15.555 to 15.686, and ²⁰⁸Pb/²⁰⁴Pb = 37.950 to 38.340). The single‐stage model ages of Group A are mainly negative or slightly positive values (‐258 to 3 Ma), while those of Group B range from 636 to 392 Ma, with an average of 495 ± 65 Ma. In addition, there are positive linear correlations among Pb isotopic ratios. These results suggest that the lead of Group A stibnite was mainly derived from the Sinian marine carbonates, and that of Group B stibnite from the underlying Lengjiaxi Group basement. This conclusion is consistent with the results of the Sr isotopes. These results indicate that the Xujiashan deposit is not syngenetic sedimentary and in situ reworked origin as previously considered. The metal (mainly Sb) of this deposit was not only derived from the Sinian host rocks, but also partly derived from the underlying Mesoproterozoic Lengjiaxi Group basement.     

Strontium and oxygen isotope decoupling in the Hercynian Trois Seigneurs Massif,Pyrenees: evidence for fluid circulation in a brittle regime

Systematic shifts of oxygen isotopic compositions in the higher grade parts of the high temperature-low pressure Hercynian metamorphic sequence, exposed in the Trois Seigneurs Massif, have previously been explained as a result of an influx of surface-derived water during the prograde part of the metamorphic cycle. It has been suggested that this caused a regional lowering of ⁸⁷Sr/⁸⁶Sr in the metamorphic sequence. Mapping of strontium isotopic compositions across a 15 m meta-carbonate horizon in the higher grade pelite-psammite sequence shows that strontium isotopic compositions were homogenised over length scales of metres or less during the Hercynian metamorphism, which brought the carbonate and pelite-psammite to oxygen isotopic equilibrium with a common fluid. Comparison of model pre-Hercynian ⁸⁷Sr/⁸⁶Sr profiles across the carbonate (based on a depositional/diagenetic age of 450 Ma and initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7086 given by 10 m length scale averaging) with the post-Hercynian ⁸⁷Sr/⁸⁶Sr profile (calculated from analysed ⁸⁷Sr/⁸⁶Sr and Rb/Sr compositions) implies strontium isotopic diffusion distances of ca. 0.4 m in the carbonate and ca. 7 m in the pelite-psammite. The limited Sr-isotopic diffusion distance of 0.4–0.7 m within the carbonate is compatible with pervasive oxygen-isotopic exchange over distances restricted to 4–15 m if fluid strontium concentrations were between 4 and 50 ppm. The strontium isotopic transport distances are not compatible with pervasive oxygen isotopic alteration over the observed 5 km regional scale. Either the flow was perfectly layer-parallel or, more probably, the regional-scale alteration of oxygen took place by fluid circulation in the brittle regime early in, or prior to, the Hercynian metamorphic event. Flow along cracks with incomplete diffusive exchange between fluid and wall rock would allow greater decoupling of oxygen and strontium isotopic transport than pervasive advective transport with local fluid-solid equilibrium.     

Geothermal waters from the Taupo Volcanic Zone,New Zealand: Li,B and Sr isotopes characterization

Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ⁷Li, δ¹¹B, ⁸⁷Sr/⁸⁶Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ⁷Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ⁷Li values (+1.4%), the other geothermal waters have a near constant δ⁷Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ¹¹B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The ⁸⁷Sr/⁸⁶Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand.