Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Contact metamorphism in the Los Santos W skarn (NW Spain)

Summary The intrusion of the Lower Permian Los Santos-Valdelacasa granitoids in the Los Santos area caused contact metamorphism of Later Vendian-Lower Cambrian metasediments. High grade mineral assemblages are confined to a 7 km wide contact aureole. Contact metamorphism was accompanied by intense metasomatism and development of skarns, and it generated the following mineral assemblages: diopside, forsterite, phlogopite (±clintonite) and humites and spinel-bearing assemblages or diopside, grossular, vesuvianite ± wollastonite in the marbles, depending on the bulk rock composition. Cordierite, K-feldspar, andalusite and, locally, sillimanite appear in the metapelitic rocks. Mineral assemblages of marbles and hornfelses indicate pressure conditions ranging from 0.2 to 0.25 GPa and maximum temperatures between 630 and 640 °C. ¹³C and ¹⁸O depletions in calcite marbles are consistent with hydrothermal fluid–rock interaction during metamorphism. Calcites are depleted in both ¹⁸O (δ¹⁸O = 12.74‰) and ¹³C (δ¹³C = −5.47‰) relative to dolomite of unmetamorphosed dolostone (δ¹⁸O = 20.79‰ and δ¹³C = −1.52‰). The δ¹³C variation can be interpreted in terms of Rayleigh distillation during continuous CO₂ fluid removal from the carbonates. The δ¹⁸O values reflect hydrothermal exchange with an externally derived fluid. Microthermometric analyses of fluid inclusions from vesuvianite indicate that the fluid was water dominated with minor contents of CO₂ (±CH₄ ± N₂) suggesting a metamorphic origin. Fluorine-bearing minerals such as chondrodite, norbergite and F-rich phlogopite indicate that contact metamorphism was accompanied by fluorine metasomatism. Metasomatism was more intense in the inner-central portion of the contact aureole, where access to fluids was extensive. The irregular geometry of the contact with small aplitic intrusives between the metasediments and the Variscan granitoids probably served as pathways for fluid circulation.     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Mineralogical and stable isotope studies of gold–arsenic mineralisation in the Sams Creek peralkaline porphyritic granite, South Island, New Zealand

At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ¹⁸O_magma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO₂) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO₂) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO₂-CH₄ + liquid H₂O ± CO₂ vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ¹⁸O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ¹⁸O (+12 to +16‰) and δ¹³C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ¹³C_{bulk carbon} values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ¹⁸O = +25‰ and δ¹³C = 0‰). Calculated δ¹⁸O_water (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ³⁴S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ³⁴S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.     

Geochemistry and mineralization age of magnesian skarn-type iron deposits of the Janggun mine, Republic of Korea

The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs₂ and −log fo₂ values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO₂ during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H⁺ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo₂ and fs₂. The δ³⁴S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated ³⁴SH_{2 S} values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ¹³C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ¹⁸OH_{2 O} and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997     

Nonsulfide zinc deposits in the Silesia–Cracow district,Southern Poland

The Silesia–Cracow district in Poland has been one of the world’s principal sources of zinc from nonsulfide zinc ore (Polish: galman). The still remaining nonsulfide ore resources can be estimated at 57 Mt at 5.6% Zn and 1.4% Pb. Nonsulfide mineralization is mainly hosted by Lower Muschelkalk (Triassic) limestone and is associated with different generations of the hydrothermal ore-bearing dolomite (OBD I, II, III). A fundamental ore control is believed to have been exerted by the basement faults, which were repeatedly reactivated during the Alpine tectonic cycle, leading to the formation of horst-and-graben structures: these dislocations may have caused short periods of emersion and the circulation of meteoric waters during the Cenozoic. Nonsulfide ores show a wide range of morphological characteristics and textures. They occur as earthy masses, crystalline aggregates, and concretions in cavities. Breccia and replacement textures are also very common. The most important mineral phases are: smithsonite, Fe–smithsonite, Zn–dolomite, goethite, and Fe–Mn(hydr)oxides. Minor hemimorphite and hydrozincite have also been detected. Two distinct nonsulfide ore types occur: the predominant red galman and the rare white galman. In the white galman, Fe–smithsonite and Zn–dolomite are particularly abundant. This ore type is commonly considered as a peripheral hydrothermal alteration product related to the same fluids that precipitated both the OBD II–III and the sulfides. In contrast, a supergene origin is commonly assumed for the red galman. Evidence of the petrographic and mineralogical difference between white and red galman is also found in stable isotope data. Smithsonite from red galman shows a limited range of δ ¹³C_VPDB values (−10.1 to −11.4‰), and δ ¹⁸O_VSMOW values (25.3‰ to 28.5‰, mean 26.8 ± 0.3‰). The uniform and low carbon isotope values of red galman smithsonite are unusual for supergene carbonate-hosted deposits and indicate the predominance of a single organic carbon source. Smithsonite from white galman has a more variable, slightly more positive carbon isotope (−2.9‰ to −7.4‰), but broadly similar oxygen isotope composition (26.8‰ to 28.9‰). The relationship of the white galman ore with the hydrothermal system responsible for OBD II and sulfide generation is still uncertain. The most important paleoweathering events took place in both Lower and Upper Silesia during Late Cretaceous up to Paleogene and early Neogene time. During this period, several short-lasting emersions and intense weathering episodes facilitated the formation of sinkholes in the Triassic carbonate rocks and the oxidation of sulfide orebodies through percolating meteoric waters. These phenomena may have lasted until the Middle Miocene.     

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.     

Gold mineralization in the Mazowe area, Harare-Bindura-Shamva greenstone belt, Zimbabwe: II. Genetic relationships deduced from mineralogical, fluid inclusion and stable isotope studies, and the Sm-Nd isotopic composition of scheelites

In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H₂O-CO₂-CH₄ fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ¹⁸O=10.8 to 13.2‰ SMOW), calcite (δ¹⁸O=9.5 to 11.9‰ SMOW and δ¹³C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ³⁴S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999     

Stable isotope characteristics and origin of ore-forming fluids in copper-gold-polymetallic deposits within strike-slip pull-apart basin of Weishan-Yongping continental collision orogenic belt, Yunnan Province, China

More than 140 middle-small sized deposits or minerals are present in the Weishan-Yongping ore concentration area which is located in the southern part of a typical Lanping strike-slip and pull-apart basin. It has plenty of mineral resources derived from the collision between the Indian and Asian plates. The ore-forming fluid system in the Weishan-Yongping ore concentration area can be divided into two subsystems, namely, the Zijinshan subsystem and Gonglang arc subsystem. The ore-forming fluids of Cu, Co deposits in the Gonglang arc fluid subsystem have δD values between −83.8‰ and −69‰, δ¹⁸O values between 4.17‰ and 10.45‰, and δ¹³C values between −13.6‰ and 3.7‰, suggesting that the ore-forming fluids of Cu, Co deposits were derived mainly from magmatic water and partly from formation water. The ore-forming fluids of Au, Pb, Zn, Fe deposits in the Zijinshan subsystem have δD values between −117.4‰ and −76‰, δ¹⁸O values between 5.32‰ and 9.56‰, and Δ¹³C values between −10.07‰ and −1.5‰. The ore-forming fluids of Sb deposits have δD values between −95‰ and −78‰, δ¹⁸O values between 4.5‰ and 32.3‰, and Δ¹³C values between −26.4‰ and −1.9‰. Hence, the ore-forming fluids of the Zijinshan subsystem must have been derived mainly from formation water and partly from magmatic water. Affected by the collision between the Indian and Asian plates, ore-forming fluids in Weishan-Yongping basin migrated considerably from southwest to northeast. At first, the Gonglang arc subsystem with high temperature and high salinity was formed. With the development of the ore-forming fluids, the Zijinshan subsystem with lower temperature and lower salinity was subsequently formed. Translated from Mineral Deposits, 2006, 25(1): 60–70 [译自: 矿床地质]     

Evolution of a Carboniferous carbonate-hosted sphalerite breccia deposit,Isle of Man

A newly discovered, extensive sphalerite-bearing breccia (~7.5 wt.% Zn) is hosted in dolomitised Carboniferous limestones overlying Ordovician–Silurian metasedimentary rocks on the Isle of Man. Although base metal sulphide deposits have been mined historically on the island, they are nearly all quartz vein deposits in the metamorphic basement. This study investigates the origin of the unusual sphalerite breccia and its relationship to basement-hosted deposits, through a combination of petrographic, cathodoluminescence, fluid inclusion, stable isotope and hydrogeologic modelling techniques. Breccia mineralisation comprises four stages, marked by episodes of structural deformation and abrupt changes in fluid temperature and chemistry. In stage I, high-temperature (T _h > 300°C), high-salinity (20–45 wt.% equiv. NaCl) fluid of likely basement origin deposited a discontinuous quartz vein. This vein was subsequently dismembered during a major brecciation event. Stages II–IV are dominated by open-space filling sphalerite, quartz and dolomite, respectively. Fluid inclusions in these minerals record temperatures of ~105–180°C and salinities of ~15–20 wt.% equiv. NaCl. The δ³⁴S values of sphalerite (6.5–6.9‰ Vienna-Canyon Diablo troilite) are nearly identical to those of ore sulphides from mines in the Lower Palaeozoic metamorphic rocks. The δ¹⁸O values for quartz and dolomite indicate two main fluid sources in the breccia’s hydrothermal system, local Carboniferous-hosted brines (~0.5–6.0‰ Vienna standard mean ocean water) and basement-involved fluids (~5.5–11.5‰). Ore sulphide deposition in the breccia is compatible with the introduction and cooling of a hot, basement-derived fluid that interacted with local sedimentary brines.     

Hypogene Zn carbonate ores in the Angouran deposit,NW Iran

The world-class Angouran nonsulfide Zn–Pb deposit is one of the major Zn producers in Iran, with resources estimated at about 18 Mt at 28% Zn, mainly in the form of the Zn carbonate smithsonite. This study aims to characterize these carbonate ores by means of their mineralogy and geochemistry, which has also been extended to the host rocks of mineralization and other local carbonate rock types, including the prominent travertines in the Angouran district, as well as to the local spring waters. Petrographical, chemical, and stable isotope (O, H, C, Sr) data indicate that the genesis of the Zn carbonate ores at Angouran is fairly distinct from that of other “classical” nonsulfide Zn deposits that formed entirely by supergene processes. Mineralization occurred during two successive stages, with the zinc being derived from a preexisting sulfide ore body. A first, main stage of Zn carbonates (stage I carbonate ore) is associated with both preexisting and subordinate newly formed sulfides, whereas a second stage is characterized by supergene carbonates (Zn and minor Pb) coexisting with oxides and hydroxides (stage II carbonate ore). The coprecipitation of smithsonite with galena, pyrite and arsenopyrite, as well as the absence of Fe- and Mn-oxides/hydroxides and of any discernible oxidation or dissolution of the sphalerite-rich primary sulfide ore, shows that the fluids responsible for the main, stage I carbonate ores were relatively reduced and close to neutral to slightly basic pH with high fCO₂. Smithsonite δ¹⁸O_VSMOW values from stage I carbonate ore range from 18.3 to 23.6‰, while those of stage II carbonate ore show a much smaller range between 24.3 and 24.9‰. The δ¹³C values are fairly constant in smithsonite of stage I carbonate ore (3.2–6.0‰) but show a considerable spread towards lower δ¹³C_VPDB values (4.6 to −11.2‰) in stage II carbonate ore. This suggests a hypogene formation of stage I carbonate ore at Angouran from low-temperature hydrothermal fluids, probably mobilized during the waning stages of Tertiary–Quaternary volcanic activity in an environment characterized by abundant travertine systems throughout the whole region. Conversely, stage II carbonate ore is unambiguously related to supergene weathering, as evidenced by the absence of sulfides, the presence of Fe-Mn-oxides and arsenates, and by high δ¹⁸O values found in smithsonite II. The variable, but still relatively heavy carbon isotope values of supergene smithsonite II, suggests only a very minor contribution by organic soil carbon, as is generally the case in supergene nonsulfide deposits.     

A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Geochemistry of C,O, and Sr isotopes and chemostratigraphy of neoproterozoic rocks in the northern Yenisei Ridge

Isotopic compositions of C, O, and Sr in carbonates, as well as Rb-Sr systems in the silicate material from Upper Precambrian and Lower Cambrian rocks exposed by the Chapa River in the northern Yenisei Ridge, are studied. The Late Precambrian part of the section includes the following formations (from the bottom to top): Lopatinskaya (hereafter, Lopatino), Vandadykskaya (hereafter, Vandadyk) or Kar’ernaya, Chivida, Suvorovskaya (hereafter, Suvorovo), Pod”emskaya (hereafter, Podyom), and Nemchanka. They are characterized by alternation of horizons with anomalously high and low δ¹³C values (such alternation is typical of the ∼700–550 Ma interval). The lower, relatively thin (20 m), positive excursion (δ¹³C up to 4.3‰) was established in dolomites from the lower subformation of the Vandadyk (Kar’ernaya) Formation (hereafter, lower Vandadyk subformation). The upper positive excursion (δ¹³C = 2.2 ± 0.6‰) was recorded in the 3-km-thick Nemchanka Formation enriched in terrigenous rocks. The lower negative excursion stands out as uniform, moderately low δ¹³C values (−2 ± 1‰) and significant thickness. It comprises the upper part of the Vandadyk Formation, as well as Chivida and Podyom formations. The upper negative excursion is related to a thin (∼20 m) marker carbonate horizon of the upper Nemchanka subformation, in which δ¹³C values fall down to −8.3‰. The lower part of the Lebyazhinskaya (hereafter, Lebyazhino) Formation, which overlies the Nemchanka Formation, shows a step-by-step increase in δ¹³C from −2.2 to 2.5‰ typical of the Vendianto-Cambrian (Nemakit-Daldyn Horizon/Stage) transitional sequences. The absence of relationships between the carbon and oxygen isotope compositions and other parameters of postsedimentary alterations suggests that the excursions characterized above could form at the sedimentation stage and coincide in general with δ¹³C fluctuations in seawater. The value of ⁸⁷Sr/⁸⁶Sr = 0.7076−0.7078 in limestones of the Podyom Formation points to their early Ediacaran age. Values of ⁸⁷Sr/⁸⁶Sr = 0.70841 and 0.70845 in dolomites of the lower Lebyazhino subformation correspond to the Early Cambrian. The Rb-Sr systems of the clay material from the Vandadyk and Chivida formations are approximated by a straight line, parameters of which correspond to the age of 695 ± 20 Ma (⁸⁷Sr/⁸⁶Sr₀ = 0.7200 ± 0.0013) and probably characterize the epigenetic stage of older sedimentary rocks, which were subjected to very rapid exhumation and “polar” sulfuric acid weathering in the course of glacioeustatic regression.     

Water-rock interactions and chemical compositional variations during ductile deformation of the NW-striking shear zone in the Jiapigou gold belt,China

Two kinds of mylonite series rocks, felsic and mafic, have been recognized in the NW-striking shear zone of the Jiapigou gold belt. During ductile deformation, a large amount of fluid interacted intensively with the mylonite series rocks: plagioclases were sericitized and theAn values declined rapidly, finally all of them were transformed to albites; dark minerals were gradually replaced by chlorites (mostly ripidolite). Meanwhile, large-scale and extensive carbonation also took place, and the carbonatization minerals varied from calcite to dolomite and ankerite with the development of deformation. The δ¹³C values of the carbonates are −3.0‰ – −5.6‰ suggesting a deep source of carbon. The ductile deformation is nearly an iso-volume one (f _v≈1). With the enhancement of shear deformation, SiO₂ in the two mylonite series rocks was depleted, while volatile components suchs as CO₂ and H₂O, and some ore-forming elements such as Au and S were obviously enriched. But it is noted that the enrichment of Au in both the mylonite series rocks did not reach the paygrade of gold. The released SiO₂ from water-rock interactions occurred in the form of colloids and absorbed gold in the fluid. When brittle structures were formed locally in the ductile shear zone, the ore-forming fluids migrated to the structures along microfractures, and preciptated auriferous quartz because of reduction of pressure and temperature. Fluid inclusion study shows that the temperature and pressure of the ore-forming fluids are 245–292°C and 95.4–131.7 MPa respectively; the salinity is 12.88–16.33wt% NaCl; the fluid-phase is rich in Ca²⁺, K⁺, Na⁺, Mg²⁺, F⁻ and Cl⁻, while the gaseous phases are rich in CO₂ and CH₄. The δD and δ¹⁸O, values of the ore-forming fluid are −84.48‰ – −91.73‰ and −0.247‰ – +2.715‰ respectively, suggesting that the fluid is composed predominantly of meteoric water. This project is financially supported by the National Natural Science Foundation of China (No. 9488010).     

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo)

The sediment-hosted stratiform Cu–Co mineralization of the Luiswishi and Kamoto deposits in the Katangan Copperbelt is hosted by the Neoproterozoic Mines Subgroup. Two main hypogene Cu–Co sulfide mineralization stages and associated gangue minerals (dolomite and quartz) are distinguished. The first is an early diagenetic, typical stratiform mineralization with fine-grained minerals, whereas the second is a multistage syn-orogenic stratiform to stratabound mineralization with coarse-grained minerals. For both stages, the main hypogene Cu–Co sulfide minerals are chalcopyrite, bornite, carrollite, and chalcocite. These minerals are in many places replaced by supergene sulfides (e.g., digenite and covellite), especially near the surface, and are completely oxidized in the weathered superficial zone and in surface outcrops, with malachite, heterogenite, chrysocolla, and azurite as the main oxidation products. The hypogene sulfides of the first Cu–Co stage display δ³⁴S values (−10.3‰ to +3.1‰ Vienna Canyon Diablo Troilite (V-CDT)), which partly overlap with the δ³⁴S signature of framboidal pyrites (−28.7‰ to 4.2‰ V-CDT) and have ∆³⁴S_SO4-Sulfides in the range of 14.4‰ to 27.8‰. This fractionation is consistent with bacterial sulfate reduction (BSR). The hypogene sulfides of the second Cu–Co stage display δ³⁴S signatures that are either similar (−13.1‰ to +5.2‰ V-CDT) to the δ³⁴S values of the sulfides of the first Cu–Co stage or comparable (+18.6‰ to +21.0‰ V-CDT) to the δ³⁴S of Neoproterozoic seawater. This indicates that the sulfides of the second stage obtained their sulfur by both remobilization from early diagenetic sulfides and from thermochemical sulfate reduction (TSR). The carbon (−9.9‰ to −1.4‰ Vienna Pee Dee Belemnite (V-PDB)) and oxygen (−14.3‰ to −7.7‰ V-PDB) isotope signatures of dolomites associated with the first Cu–Co stage are in agreement with the interpretation that these dolomites are by-products of BSR. The carbon (−8.6‰ to +0.3‰ V-PDB) and oxygen (−24.0‰ to −10.3‰ V-PDB) isotope signatures of dolomites associated with the second Cu–Co stage are mostly similar to the δ¹³C (−7.1‰ to +1.3‰ V-PDB) and δ¹⁸O (−14.5‰ to −7.2‰ V-PDB) of the host rock and of the dolomites of the first Cu–Co stage. This indicates that the dolomites of the second Cu–Co stage precipitated from a high-temperature, host rock-buffered fluid, possibly under the influence of TSR. The dolomites associated with the first Cu–Co stage are characterized by significantly radiogenic Sr isotope signatures (0.70987 to 0.73576) that show a good correspondence with the Sr isotope signatures of the granitic basement rocks at an age of ca. 816 Ma. This indicates that the mineralizing fluid of the first Cu–Co stage has most likely leached radiogenic Sr and Cu–Co metals by interaction with the underlying basement rocks and/or with arenitic sedimentary rocks derived from such a basement. In contrast, the Sr isotope signatures (0.70883 to 0.71215) of the dolomites associated with the second stage show a good correspondence with the ⁸⁷Sr/⁸⁶Sr ratios (0.70723 to 0.70927) of poorly mineralized/barren host rocks at ca. 590 Ma. This indicates that the fluid of the second Cu–Co stage was likely a remobilizing fluid that significantly interacted with the country rocks and possibly did not mobilize additional metals from the basement rocks.     

Cold seep deposits of Beauvoisin (Oxfordian; southeastern France) and Marmorito (Miocene; northern Italy): microbially induced authigenic carbonates

The relation of two well-known ancient carbonate deposits to hydrocarbon seepage was confirmed by this study. Archaea are found to be associated with the formation of Oxfordian seep carbonates from Beauvoisin and with a Miocene limestone from Marmorito ("tube-worm limestone"). Carbonates formed due to a mediation by archaea exhibit extremely positive or extremely negative δ¹³C_carbonate values, respectively. Highly positive values (+15‰) reflect the use of ¹³C-enriched CO₂ produced by methanogenesis. Low δ¹³C values of the Marmorito carbonates (–30‰) indicate the oxidation of seepage-derived hydrocarbons. Likewise, the δ¹³C content of specific tail-to-tail linked isoprenoids, biomarkers for archaea, was found to be strikingly depleted in these samples (as low as –115‰). The isotopic signatures corroborate that archaea were involved in the cycling of seepage-derived organic carbon at the ancient localities. Another Miocene limestone ("Marmorito limestone") shows a strong imprint of methanotrophic bacteria as indicated by δ¹³C values of carbonate as low as –40‰ and biomarker evidence. Epifluorescence microscopy and field-emission scanning electron microscopy revealed that bacterial biofilms were involved in carbonate aggregation. In addition to lucinid bivalves previously reported from both localities, we infer that sponges from Beauvoisin and tube worms from Marmorito depended on chemosynthesis as well. Low δ¹³C values of nodules related to sponge taphonomy (–27‰) indicate that sponges might have been linked to an enhanced hydrocarbon oxidation. Tube worm fossils from Marmorito closely resemble chemosynthetic pogonophoran tube worms from Recent cold seeps and are embedded in isotopically light carbonate (δ¹³C –30‰). Received: 13 October 1998 / Accepted: 5 February 1999