Ore lead and sulphur isotope pattern from the low-temperature veins of the Catalonian Coastal Ranges (NE Spain)

The lead isotopic composition of galenas from low-temperature veins of the Catalonian Coastal Ranges (NE Spain) displays a small but distinct range of values: 18.318 ≤²⁰⁶Pb/²⁰⁴Pb ≤ 18.678; 15.678 ≤²⁰⁷Pb/²⁰⁴Pb ≤ 15.767 and 38.534 ≤ ²⁰⁸Pb/²⁰⁴Pb ≤ 39.189. The data define a linear trend in the ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram that can be interpreted in terms of mixing of lead from different reservoirs. The lead appears to be derived from a solution that preferentially leached granites of Late-Hercynian age. Sulphur isotopic compositions of the galenas range from −8.5 to + 7.3‰ but variations in a single deposit are small (1–2‰), pointing to different sources of sulphur. In a δ³⁴S versus ²⁰⁶Pb/²⁰⁴Pb plot no clear correlation trends appear. Lead isotope data from deposits of similar characteristics situated within the Hercynian orogenic belt as the Linares-La Carolina district (S Spain) and the Inglesiente-Sulcis area (Sardinia) show slight differences indicating a source area of similar lead isotopic composition. In the CCR and Linares-La Carolina districts, the main source of lead is related to the Hercynian granites of each area, although small contributions from metasediments cannot be ruled out. The contribution of lead from metasedimentary rocks is particularly seen in the Sardinian (Hercynian vein-type) ores. Received: 8 August 1996 / Accepted: 5 December 1996     

From basalt to dacite: origin and evolution of the calc-alkaline series of Salina, Aeolian Arc, Italy

The island of Salina comprises one of the most distinct calc-alkaline series of the Aeolian arc (Italy), in which calc-alkaline, high-K calc-alkaline, shoshonitic and leucite-shoshonitic magma series are developed. Detailed petrological, geochemical and isotopic (Sr, Nd, Pb, O) data are reported for a stratigraphically well-established sequence of lavas and pyroclastic rocks from the Middle Pleistocene volcanic cycle (430–127 ka) of Salina, which is characterized by an early period of basaltic volcanism (Corvo; Capo; Rivi; Fossa delle Felci, group 1) and a sequence of basaltic andesites, and andesites and dacites in the final stages of activity (Fossa delle Felci, groups 2–8). Major and trace element compositional trends, rare earth element (REE) abundances and mineralogy reveal the importance of crystal fractionation of plagioclase + clinopyroxene + olivine/ orthopyroxene ± titanomagnetite ± amphibole ± apatite in generating the more evolved magma types from parental basaltic magmas, and plagioclase accumulation in producing the high Al₂O₃ contents of some of the more evolved basalts. Sr isotope ratios range from 0.70410 to 0.70463 throughout the suite and show a well-defined negative correlation with ¹⁴³Nd/¹⁴⁴Nd (0.51275–0.51279). Pb isotope compositions are distinctly radiogenic with relatively large variations in ²⁰⁶Pb/²⁰⁴Pb (19.30–19.66), fairly constant ²⁰⁷Pb/²⁰⁴Pb (15.68–15.76) and minor variations in ²⁰⁸Pb/²⁰⁴Pb ratios (39.15–39.51). Whole-rock δ¹⁸O values range from +6.4 to +8.5‰ and correlate positively with Sr isotope ratios. Overall, the isotopic variations are correlated with the degree of differentiation of the rocks, indicating that only small degrees of crustal assimilation are overprinting the dominant evolution by crystal–liquid fractionation (AFC-type processes). The radiogenic and oxygen isotope composition of the Salina basalts suggests derivation from primary magmas from a depleted mantle source contaminated by slab-derived fluids and subducted sediments with an isotopic signature of typical upper continental crust. These magmas then evolved further to andesitic and dacitic compositions through the prevailing process of low-pressure fractional crystallization in a shallow magma reservoir, accompanied by minor assimilation of crustal lithologies similar to those of the Calabrian lower crust. Received: 29 November 1999 / Accepted: 16 April 2000     

Distinguishing magmatic from subsolidus epidote: laser probe oxygen isotope compositions

Epidote occurs in four textural varieties in the Mount Lowe intrusion of southern California: euhedra, anhedra, intergrowths and cross-cutting veins. Of these, conspicuous elongate euhedra, which range up to 3 cm in length, meet most of the established textural criteria for magmatic epidote. Equant anhedral grains, which are ˜5 mm in diameter, are texturally ambiguous although rare allanite cores are suggestive of a magmatic origin. Epidote intergrowths with hornblende and biotite also meet certain textural criteria for crystallization from a magma, notably, euhedral faces against biotite. Finally, late-stage veins of epidote cross-cut all phases in the rock and are likely subsolidus. Oxygen isotopic compositions of these four textural varieties of epidote determined using the laser probe indicate that the use of textural criteria alone in establishing epidote parageneses can be misleading. Intracrystalline δ¹⁸O variations in the euhedra document both magmatic and subsolidus compositions. Oxygen isotope compositions are bimodal averaging 5.36 ± 0.13‰ (n = 11) and 4.66 ± 0.23‰ (n = 21). These data combined with plagioclase and zircon δ¹⁸O values are interpreted to indicate that magmatic oxygen isotopic compositions have been preserved where epidote δ¹⁸O is greater than 5‰. Significant portions of each euhedral crystal have been affected by subsolidus exchange and are characterized by epidote δ¹⁸O values less than 5‰. Intracrystalline δ¹⁸O values of epidote anhedra range from 4.50 to 6.08‰ and thus also document both magmatic and subsolidus compositions. Subsolidus exchange is volumetrically less significant in the anhedra than in the euhedra. Values of δ¹⁸O for intergrowths and late-stage cross-cutting veins of epidote average 3.81 ± 0.22‰ and document clearly subsolidus growth. The data confirm that in the Mount Lowe intrusion, large euhedra of epidote are magmatic in origin, consistent with textural evidence. The data also indicate that equant anhedra of epidote are also magmatic in origin and thus the absence of good crystal faces does not necessarily indicate subsolidus growth. The subsolidus origin of intergrowths of epidote with euhedral faces against biotite indicates that well developed crystal faces do not require growth from a magma. Finally, the subsolidus origin of the vein epidote is consistent with textural evidence. The increased resolution available with laser-based oxygen isotope measurements offers an important test for documenting whether epidote is of magmatic or subsolidus origin. Given the barometric significance of magmatic epidote, oxygen isotope compositions can be used to aid in the interpretation of epidote-bearing plutons. Received: 9 April 1996 / Accepted: 3 August 1996     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Metamorphism, isotopic ages and composition of lower crustal granulite xenoliths from the Cretaceous Salta Rift, Argentina

Crustal xenoliths from basanitic dikes and necks that intruded into continental sediments of the Cretaceous Salta Rift at Quebrada de Las Conchas, Provincia Salta, Argentina were investigated to get information about the age and the chemical composition of the lower crust. Most of the xenoliths have a granitoid composition with quartz-plagioclase-garnet-rutile ± K-feldspar as major minerals. The exceedingly rare mafic xenoliths consist of plagioclase-clinopyroxene-garnet ± hornblende. All xenoliths show a well equilibrated granoblastic fabric and the minerals are compositionally unzoned. Thermobarometric calculations indicate equilibration of the mafic xenoliths in the granulite facies at temperatures of ca. 900 °C and pressures of ca. 10 kbar. The Sm-Nd mineral isochron ages are 95.1 ± 10.4 Ma, 91.5 ± 13.0 Ma, 89.0 ± 4.2 Ma (granitoid xenoliths), and 110.7 ± 23.6 Ma (mafic xenolith). These ages are in agreement with the age of basanitic volcanism (ca. 130–100 and 80–75 Ma) and are interpreted as minimum ages of metamorphism. Lower crustal temperature at the time given by the isochrons was above the closure temperature of the Sm-Nd system (>600–700 °C). The Sm-Nd and Rb-Sr isotopic signatures (¹⁴⁷Sm/¹⁴⁴Nd = 0.1225–0.1608; ¹⁴³Nd/¹⁴⁴Nd_{t 0} = 0.512000–0.512324; ⁸⁷Rb/⁸⁶Sr = 0.099–0.172; ⁸⁷Sr/⁸⁶Sr_{t 0} = 0.708188–0.7143161) and common lead isotopic signatures (²⁰⁶Pb/²⁰⁴Pb = 18.43–18.48; ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.70; ²⁰⁸Pb/²⁰⁴Pb = 38.22 –38.97) of the granitoid xenoliths are indistinguishable from the isotopic composition of the Early Paleozoic metamorphic basement from NW Argentina, apart from the lower ²⁰⁸Pb/²⁰⁴Pb ratio of the basement. The Sm-Nd depleted mantle model ages of ca. 1.8 Ga from granitoid xenoliths and Early Paleozoic basement point to a similar Proterozoic protolith. Time constraints, the well equilibrated granulite fabric, P-T conditions and lack of chemical zoning of minerals point to a high temperature in a crust of nearly normal thickness at ca. 90 Ma and to a prominent thermal anomaly in the lithosphere. The composition of the xenoliths is similar to the composition of the Early Paleozoic basement in the Andes of NW Argentina and northern Chile. A thick mafic lower crust seems unlikely considering low abundance of mafic xenoliths and the predominance of granitoid xenoliths. Received: 21 July 1998 / Accepted: 27 October 1998     

Geochemistry of bedded barite of the Mesoproterozoic Aggeneys-Gamsberg Broken Hill-type district,South Africa

Stratiform and stratabound barite ± magnetite beds are intimately associated with the polymetallic Broken Hill-type (BHT) massive sulfide deposits of the Aggeneys-Gamsberg Pb–Zn–Cu ± Ag–Ba district in the Northern Cape Province, South Africa. Barite samples were collected and studied from four localities in the district. Although metamorphic water–rock interaction processes have partially altered the chemical and to a lesser degree the isotopic composition of barite, samples identified as being the least altered display distinctly different isotopic compositions that are thought to reflect different modes of origin. All barite samples are marked by low concentrations of SrO (0.5 ± 0.2 wt%), highly radiogenic ⁸⁷Sr/⁸⁶Sr ratios, elevated δ ³⁴S and δ ¹⁸O values compared to contemporaneous Mesoproterozoic seawater. Radiogenic ⁸⁷Sr/⁸⁶Sr signatures (0.7164 ± 0.0028) point to an evolved continental crustal source for Sr and Ba, while elevated δ ³⁴S values (27.3 ± 4.9‰) indicate that contemporaneous seawater sulfate, modified by bacterial sulfate reduction, was the single most important sulfur reservoir for barite deposition. Most importantly, δ ¹⁸O values suggest a lower temperature of formation for the Gamsberg deposit compared with the occurrences in the Aggeneys area, i.e. Swartberg-Tank Hill and Big Syncline. The obvious differences in temperature of formation are in good agreement with the Cu-rich, Ba-poor nature of the sulfide mineralization of the Aggeneys deposits vs the Cu-poor, Ba-rich character of the Gamsberg deposit. In conjunction with this, isotopic and petrographic arguments favor a sub-seafloor replacement model for the stratabound barite occurrences of the Aggeneys deposits, while at Gamsberg, deposition at the sediment–water interface as a true sedimentary exhalite appears more likely.     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Thermal and chemical evolution of fluids during fluorite deposition in the Zaghouan province, north-eastern Tunisia

Several F, Pb, Zn and Ba deposits are located in the province of Zaghouan in north-eastern Tunisia. They are hosted in Lower Liassic or Upper Jurassic reef limestones, and the overlying condensed Carixian phosphatic limestones and Campanian marls, respectively. The mineralization occurs in three types of orebodies: stratiform replacement heaps and lenses (Jebel Stah and Hammam Zriba), breccia fillings and dissolution void fillings (Sidi Taya) and lodes (Jebel Oust). More than one generation of fluorite is observed in the stratiform deposits. Microthermometric analyses of the inclusion fluids observed in fluorite and quartz show that the economic concentrations of fluorite have deposited from moderate to highly saline (12–22.5 wt% NaCl equivalents) hydrothermal (110–160 °C) mineralizing fluids at the center (Jebel Stah, Sidi Taya) and to the east of the province (Hammam Zriba). Late remobilizations, observed in the stratiform deposits, are related to the circulation of a warmer (up to 185 °C) but less saline (10 wt% NaCl equivalents) fluid (Jebel Stah) and more saline (12–22 wt% NaCl equivalents) fluid (Hammam Zriba). The highest temperature (up to 250 °C) and salinity (32–34 wt% NaCl equivalents) are observed to the west of the province of Zaghouan (Jebel Oust). Less saline (3–6 wt% NaCl equivalents) and moderately hot to hot fluids (up to 220 ± 20 °C) and rich in gaseous CO₂ invade most of the ore deposits in later stages and give rise to the massive quartz within fractures at Jebel Stah. Chemical analyses of the fluids extracted from the inclusions occuring in fluorite show compositions dominated by the presence of Na⁺, Ca²⁺ and Cl⁻ ionic species and allow the mean temperature of the fluids in the source reservoir to be estimated as 275 ± 25 °C. The circulation of the ore-forming fluids is triggered by a regional tectonic extensional phase which occurs within the post-Jurassic to ante-Miocene time interval. The deposition of the economic concentrations of fluorite resulted from the decrease in pressure and temperature of the hydrothermal brines (Jebel Oust), along with the increase in the dissolved calcium activity (Jebel Stah and Sidi Taya), or a decrease in salinity due to the mixing with a hot, less saline and Na-poor, Ca-rich fluid (Hammam Zriba). The mineralogical associations (CaF₂, PbS, ZnS, BaSO₄) hosted within carbonate rocks, the temperatures and the salinities of the fluids that gave rise to the more important ore deposits (110–160 °C and 12–22.5 wt% NaCl equivalents), their composition (Na, Ca, Cl) and the molar ratios between the major ionic species, as well as the presence of liquid hydrocarbons in the mineralizing fluids, show that the ore deposits of the province of Zaghouan belong to the carbonate-hosted F, Pb, Zn, Ba Mississippi Valley-type deposits. Received: 23 June 1995 / Accepted: 18 November 1996     

Oxygen isotopes composition of sapphires from the French Massif Central: implications for the origin of gem corundum in basaltic fields

Alluvial and colluvial gem sapphires are common in the basaltic fields of the French Massif Central (FMC) but sapphire-bearing xenoliths are very rare, found only in the Menet trachytic cone in Cantal. The O-isotope composition of the sapphires ranges between 4.4 and 13.9‰. Two distinct groups have been defined: the first with a restricted isotopic range between 4.4 and 6.8‰ (n = 22; mean δ¹⁸O = 5.6 ± 0.7‰), falls within the worldwide range defined for blue-green-yellow sapphires related to basaltic gem fields (3.0 < δ¹⁸O < 8.2‰, n = 150), and overlaps the ranges defined for magmatic sapphires in syenite (4.4 < δ¹⁸O < 8.3‰, n = 29). A second group, with an isotopic range between 7.6 and 13.9‰ (n = 9), suggests a metamorphic sapphire source such as biotite schist in gneisses or skarns. The δ¹⁸O values of 4.4–4.5‰ for the blue sapphire-bearing anorthoclasite xenolith from Menet is lower than the δ¹⁸O values obtained for anorthoclase (7.7–7.9‰), but suggest that these sapphires were derived from an igneous reservoir in the subcontinental spinel lherzolitic mantle of the FMC. The presence of inclusions of columbite-group minerals, pyrochlore, Nb-bearing rutile, and thorite in these sapphires provides an additional argument for a magmatic origin. In the FMC lithospheric mantle, felsic melts crystallized to form anorthoclasites, the most evolved peraluminous variant of the alkaline basaltic melt. The O-isotopic compositions of the first group suggests that these sapphires crystallized from felsic magmas under upper mantle conditions. The second group of isotopic values, typified for example by the Le Bras sapphire with a δ¹⁸O of 13.9‰, indicates that metamorphic sapphires from granulites were transported to the surface by basaltic magma.     

Sulfur, lead and helium isotopic compositions of sulfide minerals from the Dachang Sn-polymetallic ore district in South China: implication for ore genesis

Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ³⁴S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ³⁴S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ³⁴S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb or ²⁰⁸Pb/²⁰⁴Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The ³He/⁴He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

Isotopic and chemical intra-shell variations in low-Mg calcite of rudist bivalves (Mollusca-Hippuritacea): disequilibrium fractionations and late Cretaceous seasonality

 Isotopic (δ¹³C, δ¹⁸O) and elemental (Mg, Sr, Mn, Fe) compositions were analysed in sclerochronological profiles of several shells of late Cretaceous rudist bivalves from Greece, Turkey, Somalia and the Arabian Peninsula. The preservation of original compositions of low-Mg calcite of outer shell layers is indicated by constant and high Sr, generally low Fe and Mn, and the preservation of fibrous-prismatic ultrastructures. Cyclic variations in δ¹⁸O and Mg are interpreted to reflect seasonal temperature/salinity cycles and, thus, annual growth increments. In shells of Torreites, amplitudes of correlated δ¹³C and δ¹⁸O cycles cannot be related to reasonable palaeotemperatures or salinity. This isotopic pattern reflects vital fractionations of an extent which is unknown from modern bivalves. In contrast, almost identical ranges and amplitudes of δ¹⁸O cycles are observed in 13 shells of five species from Santonian-Campanian localities in central Greece and northern Turkey, suggesting that seasonal variations in environmental conditions were recorded without significant vital fractionations. The effect of seasonal salinity changes on δ¹⁸O of the shells is evaluated, and mean palaeotemperatures are constrained within the range of 30–32.5  °C. The annual range of temperature was estimated to be 7  °C, assuming a constant salinity. This agrees with other isotopic proxies of Late Cretaceous palaeotemperatures, and with global circulation models which predict higher low-latitude sea-surface temperatures than the present ones. Received: 12 February 1998 / Accepted: 24 May 1999     

Mobilization of Ag,heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería,SE Spain)

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg^–1), Ba (mean 2.5%), Fe (mean 114,000 mg kg^–1), Sb (mean 342.5 mg kg^–1), Pb (mean 1,229.8 mg kg^–1), Zn (mean 493 mg kg^–1), Mn (mean 4,321.1 mg kg^–1), Cd (mean 1.2 mg kg^–1) and Eu (mean 4.0 mg kg^–1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)₃, which controls the solubility of Eu in the pH–Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.     

Large crustal input to high δ18O anorthosite massifs of the southern Grenville Province: new evidence from the Morin Complex, Quebec

Mid-Proterozoic anorthosite-suite magmatism is a major volumetric component of the southern Grenville Province, and provides an important probe of the compositions and types of lower crustal rocks. The ∼1.15 Ga Morin Complex (Quebec) consists of two anorthosite plutons with distinct compositions. Plagioclase from the western lobe of the anorthosite has δ¹⁸O values that average 9.6 ± 0.7‰, which is ∼3‰ higher than the values found in “normal” anorthosites and in mantle-derived mafic igneous rocks worldwide. Plagioclase from the eastern lobe of the massif (deformed by the Morin Shear Zone) has δ¹⁸O values that average 8.7 ± 0.6‰, also high compared to mantle-derived rocks. Numerous lines of evidence, including homogeneity of δ¹⁸O values within individual plutons, O–Sr–Nd mixing relations, and preservation of igneous δ¹⁸O in adjacent mangerite units argue against anorthosite interaction with high δ¹⁸O fluids as the cause of the high δ¹⁸O values seen in both anorthosite lobes. High δ¹⁸O values are best explained as primary magmatic compositions resulting from melting and assimilation of crustal materials by the anorthosite's parent magma. The Morin and Marcy massifs are located in the Allochthonous Monocyclic Belt of the Grenville Province, and have the highest known δ¹⁸O values for anorthosites in the Grenville. Although the Monocyclic Belt is juvenile in terms of radiogenic isotope systematics, the new oxygen isotope data indicate the presence high δ¹⁸O supracrustal materials at the base of the crust, probably buried during the ∼1.2 Ga Elzevirian orogeny in the Monocyclic Belt prior to anorthosite magmatism. This process is not recognized in other parts of the Grenville Province and points to differences in the pre-1.2-Ga continental margins. Received: 29 September 1999 / Accepted: 7 March 2000     

Hydrothermal carbonates in altered wall rocks at the Uwamuki Kuroko deposits, Japan

Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ¹⁸O and δ¹³C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997     

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

Summary We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes “fassaitic” clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (T_HOM = 1000–1050 °C), b) CO₂ ± H₂S-rich fluid inclusions (T_HOM = 20–31.3 °C into the vapor phase), c) multiphase aqueous brine inclusions (T_HOM = 720–820 °C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (T_HOM = 870–890 °C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt – aqueous chloride-rich liquid – carbonate/sulfate melt?) during heating and cooling below 870 °C. There is no evidence for fluid circulation below 700 °C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable ²⁰⁶Pb/²⁰⁴Pb (19.047–19.202), ²⁰⁷Pb/²⁰⁴Pb (15.655–15.670), and ²⁰⁸Pb/²⁰⁴Pb (38.915–39.069) and relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51211–0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (δ¹³C_V-PDB = −5.4 to −1.1‰; δ18O_V-SMOW = 11.7 to 16.4‰) indicate formation from a ¹⁸O- and ¹³C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO₂-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns. Received March 1, 2000; revised version accepted November 2, 2000     

Plutonism in the Variscan Odenwald (Germany): from subduction to collision

 Latest Devonian to early Carboniferous plutonic rocks from the Odenwald accretionary complex reflect the transition from a subduction to a collisional setting. For ∼362 Ma old gabbroic rocks from the northern tectonometamorphic unit I, initial isotopic compositions (ε_Nd=+3.4 to +3.8;⁸⁷Sr/⁸⁶Sr =0.7035–0.7053;δ¹⁸O=6.8–8.0‰) and chemical signatures (e.g., low Nb/Th, Nb/U, Ce/Pb, Th/U, Rb/Cs) indicate a subduction-related origin by partial melting of a shallow depleted mantle source metasomatized by water-rich, large ion lithophile element-loaded fluids. In the central (unit II) and southern (unit III) Odenwald, syncollisional mafic to felsic granitoids were emplaced in a transtensional setting at approximately 340–335 Ma B.P. Unit II comprises a mafic and a felsic suite that are genetically unrelated. Both suites are intermediate between the medium-K and high-K series and have similar initial Nd and Sr signatures (ε_Nd=0.0 to –2.5;⁸⁷Sr/⁸⁶Sr=0.7044–0.7056) but different oxygen isotopic compositions (δ¹⁸O=7.3–8.7‰ in mafic vs 9.3–9.5‰ in felsic rocks). These characteristics, in conjunction with the chemical signatures, suggest an enriched mantle source for the mafic magmas and a shallow metaluminous crustal source for the felsic magmas. Younger intrusives of unit II have higher Sr/Y, Zr/Y, and Tb/Yb ratios suggesting magma segregation at greater depths. Mafic high-K to shoshonitic intrusives of the southern unit III have initial isotopic compositions (ε_Nd=–1.1 to –1.8;⁸⁷Sr/⁸⁶Sr =0.7054–0.7062;δ¹⁸O=7.2–7.6‰) and chemical characteristics (e.g., high Sr/Y, Zr/Y, Tb/Yb) that are strongly indicative of a deep-seated enriched mantle source. Spatially associated felsic high-K to shoshonitic rocks of unit III may be derived by dehydration melting of garnet-rich metaluminous crustal source rocks or may represent hybrid magmas. Received: 7 December 1998 / Accepted: 27 April 1999     

The Darasun gold deposit,Eastern Transbaikal region: Chemical composition,REE patterns,and stable carbon and oxygen isotopes of carbonates from ore veins

The chemistry, REE patterns, and carbon and oxygen isotopic compositions of carbonates from ore veins of the Darasun deposit are discussed. In addition to the earlier described siderite, calcite, and carbonates of the dolomite-ankerite series, kutnahorite is identified. The total REE content in Fe-Mg carbonates of the dolomite-ankerite series (2.8–73 ppm) is much lower than in later calcite (18–390 ppm). δ¹³C of Fe-Mg carbonates and calcite varies from +1.1 to −6.7‰ and from −0.9 to −4.9‰, respectively. δ¹⁸O of Fe-Mg carbonates and calcite varies from +17.6 to 3.6‰ and from +15.7 to −0.5‰, respectively. The REE sum and carbon and oxygen isotopic compositions reveal zonal distribution relative to the central granodiorite porphyry stock. The correlation between the carbon and oxygen isotopic compositions and REE sum reflects variations in the physicochemical formation conditions and composition of ore-forming fluid. The isotopic composition of fluid is calculated, and possible sources of its components are considered. Earlier established evidence for a magmatic source of ore-forming fluid and participation of meteoric water in ore formation is confirmed. Geochemical evidence for interaction of ore-forming fluid with host rocks is furnished. The relationships between the REE sum, on the one hand, and carbon and oxygen isotopic compositions of hydrothermal ore-forming fluid, on the other, are established.     

Prograde and retrograde fluid-rock interaction in calc-silicates northwest of the Idaho batholith: stable isotopic evidence

Carbon and oxygen isotopic analyses of silicate and carbonate minerals indicate that isotopic compositions in metasediments of the Wallace Formation (Belt Supergroup) exposed northwest of the Idaho batholith have been affected by both prograde and retrograde fluid-rock interaction. Silicates retain isotopic fractionations that reflect equilibration at peak metamorphic temperatures. In contrast, calcite oxygen isotopic compositions range from δ¹⁸O(Calcite)=+2.3 to +18.6‰ SMOW (standard mean oceanic water) and indicate that some calcites have exchanged with low-δ¹⁸O meteorichydrothermal fluids. Values of Δ¹⁸O (Quartz-Calcite) as large as +15.5 clearly indicate that the isotopic depletion of these calcites postdates the peak of regional metamorphism. Carbon isotopic compositions of ¹⁸O-depleted calcites are not significantly shifted relative to δ¹³C values in undepleted calcites, suggesting that the retrograde fluid was carbon-poor. Petrographically, retrograde fluid-rock interaction is associated with the occurrence of fine-grained, highly-luminescent calcite overgrowths on less-luminescent, metamorphic calcites, slight to moderate argillic alteration, and pseudomorphing of scapolite porphyroblasts by fine-grained albite. Retrograde isotopic depletions may be related to shallow meteoric-hydrothermal fluid flow developed around the Idaho batholith after intrusion and rapid uplift of the terrane. Peak metamorphic isotopic compositions in the Wallace Formation reflect mineralogically heterogeneous protolith compositions and isotopic fractionation due to devolatilization and/or infiltration. Variability in oxygen isotopic compositions on the order of 4–6‰ within the same rock type can be attributed to the combined effects of inherited isotopic compositions and isotopic shifts resulting from prograde devolatilization. Isotopic and compositional heterogeneity on the scale of mm to m precludes generalization of isotopic gradients on a regional scale. The isotopic data presented here, and metamorphic fluid compositions determined in previous studies, are best reconciled with heterogeneous bulk compositions, dominantly channelized prograde and retrograde fluid flow, and locally low fluid-rock ratios.