A comparative study on isotopic composition of precipitation in wet tropic and semi-arid stations across southern India

Isotopic composition of monthly composite precipitation samples from Kozhikode (n = 31), a wet tropic station and Hyderabad (n = 25), a semi-arid station across southern India were studied for a period of four years from 2005 to 2008. During the study period, the Kozhikode station recorded an average rainfall of 3500 mm while the Hyderabad station showed an average rainfall of 790 mm. The average stable isotope values in precipitation at the Kozhikode station were δ ¹⁸O = −3.52‰, d-excess = 13.72‰; δ ¹⁸O = −2.94‰, d-excess = 10.57‰; and δ ¹⁸O = −7.53‰, d-excess = 13.79‰, respectively during the pre-monsoon (March–May), monsoon (June–September) and post-monsoon (October–February) seasons. For the Hyderabad station, the average stable isotope values were δ ¹⁸O = −5.88‰, d-excess = 2.34‰; δ ¹⁸O = −4.39‰, d-excess = 9.21‰; and δ ¹⁸O = −8.69‰, d-excess = 14.29‰, respectively for the three seasons. The precipitation at the two stations showed distinctive isotopic signatures. The stable isotopic composition of precipitation at the Hyderabad station showed significant variations from the global trend while the Kozhikode station almost followed the global value. These differences are mainly attributed to the latitudinal differences of the two stations coupled with the differences in climatic conditions.     

Oxygen isotope systematics of emerald: relevance for its origin and geological significance

Oxygen isotopic composition of emerald from 62 occurrences and deposits in the world reveals a wide range in δ¹⁸O (SMOW) between +6.2 and +24.7‰. The δ¹⁸O-values for each deposit are restricted and can be used to determine the origin of emerald from the world's most important producers. The δ¹⁸O-value of emerald appears to be a fingerprint of its origin, especially for gems of exceptional quality from Colombia (eastern emerald zone, δ¹⁸O = +16.8 ± 0.1‰; western emerald zone, δ¹⁸O = +21.2 ± 0.5‰), Afghanistan (δ¹⁸O = +13.5 ± 0.1‰), Pakistan (Swat-Mingora districts, δ¹⁸O = +15.7 ± 0.1‰), Brazil (Santa Terezinha de Goiás, δ¹⁸O = +12.2 ± 0.1‰; Quadrilatero Ferrifero, δ¹⁸O = +6.9 ± 0.4‰) and Zimbabwe (Sandawana, δ¹⁸O = +7.5 ± 0.5‰). Furthermore, the ¹⁸O-composition of emerald appears to be a good marker of its geological environment because the data suggest that host-rock-buffering of fluid δ¹⁸O is considerable during fluid-rock interaction. Received: 29 January 1998 / Accepted: 25 March 1998     

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.     

Stable water isotope climate archives in springs from the Olympic Mountains,Washington

The ¹⁸O and ²H (HDO) compositions are summarized for sampled springs (n = 81) within the Elwha watershed (≈692 km²) on the northern Olympic Peninsula. Samples, collected during 2001–2009, of springs (n = 158), precipitation (n = 520), streams (n = 176), and firn (n = 3) assisted the determinations for meteoric composition of recharge waters. The local mean water line (LMWL) is defined as δ²H = 8.2δ¹⁸O − 9.3 for the watershed. Recharge history is surmised from groundwater ages ranging from 5 ± 3 years (apparent ⁸⁵Kr) to 9,490 ± 420 ¹⁴C cal years BP. About 56% of the springs were recharged over the last 1,000 years while 13% of springs were recharged over 5,000 years ago. Spring HDO values fluctuate between −11.8 to −15.6‰ δ¹⁸O and −90.9 to −119.4‰ δ²H. Deuterium excess values predominate around 4–6‰. The HDO proxy records from springs suggest a pronounced paleoclimate shift in air masses near 5,000 year BP on the Peninsula.     

Spatio-temporal variations of δ<Superscript>2</Superscript>H and δ<Superscript>18</Superscript>O in precipitation and shallow groundwater in the Hilly Loess Region of the Loess Plateau,China

Groundwater is of utmost significance to socio-economic development and ecological recovery for the Loess Plateau. However, studies regarding the mechanism governing groundwater recharge over this area appear to be inadequate. This study is to examine the spatio-temporal variations of δ²H and δ¹⁸O in precipitation and shallow groundwater. On the basis of this, the mechanisms governing shallow groundwater recharge were explored. Precipitation and groundwater were sampled monthly from May to October during the period 2004–2006 at 13 sites in the Chabagou Catchment (187 km²). In the Caopingxigou Experimental Watershed (0.1 km²), meteorological variables were observed and rainfall larger than 5 mm was sampled immediately after each rain event. Across the area, 90% of the precipitation occurred from May to September primarily in the form of heavy rains or rainstorms with great spatial variability. There were about 30 localized rains in each year. It was indicated that there existed notable seasonality and pronounced spatial variability in precipitation isotopic compositions. Contributing factors and indications of isotopic compositions, as well as their climatic indications such as monsoon intensities and mixing processes of water vapor, were investigated. The δ²H–δ¹⁸O relation of groundwater was found to be δ²H = 3.22 × δ¹⁸O − 38.1, deviating from the local meteoric water line δ²H = 7.57 × δ¹⁸O + 3.9. The range of δ values in groundwater is shrunken to be 15–21% of that in individual precipitations, and groundwater in the middle reaches shows a wider range of δ values. Isotopic results showed that groundwater originates from precipitation with hydrogen and oxygen isotopic compositions being −69 and −9.7‰, respectively, and most groundwater experiences serious evaporation and adequate mixing with old water during infiltration or percolation in the aerated zone. It was also founded that obvious fluctuations of isotopic compositions in groundwater mainly appear in the middle reaches especially at sites that are close to valleys, suggesting varying sources of groundwater from precipitation, precipitation runoff, isotopically enriched surface water and/or lateral recharge of adjacent groundwater.     

Geology and vein tin mineralization in the Dadoushan deposit,Gejiu district,SW China

Vein-type tin mineralization in the Dadoushan deposit, Laochang ore field, Gejiu district, SW China, is predominantly hosted in Triassic carbonate rocks (Gejiu Formation) over cupolas of the unexposed Laochang equigranular granite intrusion. The most common vein mineral is tourmaline, accompanied by skarn minerals (garnet, diopside, epidote, phlogopite) and beryl. The main ore mineral is cassiterite, accompanied by minor chalcopyrite, pyrrhotite, and pyrite, as well as scheelite. The tin ore grade varies with depth, with the highest grades (~1.2 % Sn) prevalent in the lower part of the vein zone. Muscovite ⁴⁰Ar–³⁹Ar dating yielded a plateau age of 82.7 ± 0.7 Ma which defines the age of the vein-type mineralization. Measured sulfur isotope compositions (δ ³⁴S = −4.1 to 3.9 ‰) of the sulfides (arsenopyrite, chalcopyrite, pyrite, and pyrrhotite) indicate that the sulfur in veins is mainly derived from a magmatic source. The sulfur isotope values of the ores are consistent with those from the underlying granite (Laochang equigranular granite, −3.7 to 0.1 ‰) but are different from the carbonate wall rocks of the Gejiu Formation (7.1 to 11.1 ‰). The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (δ ¹⁸O_H2O = −2.4 to 5.5 ‰, δD = −86 to −77 ‰) suggest an initially magmatic fluid which gradually evolved towards meteoric water during tin mineralization.     

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.     

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     

Mineralogical, fluid inclusion, and stable isotope constraints on mechanisms of ore deposition at the Samgwang mine (Republic of Korea)—a mesothermal, vein-hosted gold–silver deposit

The Samgwang mine is located in the Cheongyang gold district (Cheonan Metallogenic Province) of the Republic of Korea. It consists of eight massive, gold-bearing quartz veins that filled NE- and NW-striking fractures along fault zones in Precambrian granitic gneiss of the Gyeonggi massif. Their mineralogy and paragenesis allow two separate vein-forming episodes to be recognized, temporally separated by a major faulting event. The ore minerals occur in quartz and calcite of stage I, associated with fracturing and healing of veins. Hydrothermal wall-rock alteration minerals of stage I include Fe-rich chlorite (Fe/(Fe+Mg) ratios 0.74-0.81), muscovite, illite, K-feldspar, and minor arsenopyrite, pyrite, and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, argentite, pyrargyrite, and argentian tetrahedrite. Only calcite was deposited during stage II. Fluid inclusions in quartz contain three main types of C–O–H fluids: CO₂-rich, CO₂–H₂O, and aqueous inclusions. Quartz veins related to early sulfides in stage I were deposited from H₂O–NaCl–CO₂ fluids (1,500–5,000 bar, average 3,200) with T _htotal values of 200°C to 383°C and salinities less than about 7 wt.% NaCl equiv. Late sulfide deposition was related to H₂O–NaCl fluids (140–1,300 bar, average 700) with T _htotal values of 110°C to 385°C and salinities less than about 11 wt.% NaCl equiv. These fluids either evolved through immiscibility of H₂O–NaCl–CO₂ fluids as a result of a decrease in fluid pressure, or through mixing with deeply circulated meteoric waters as a result of uplift or unloading during mineralization, or both. Measured and calculated sulfur isotope compositions (δ³⁴S_H2S = 1.5 to 4.8‰) of hydrothermal fluids from the stage I quartz veins indicate that ore sulfur was derived mainly from a magmatic source. The calculated and measured oxygen and hydrogen isotope compositions (δ¹⁸O_H2O = −5.9‰ to 10.9‰, δD = −102‰ to −87‰) of the ore-forming fluids indicate that the fluids were derived from magmatic sources and evolved by mixing with local meteoric water by limited water–rock exchange and by partly degassing in uplift zones during mineralization. While most features of the Samgwang mine are consistent with classification as an orogenic gold deposit, isotopic and fluid chemistry indicate that the veins were genetically related to intrusions emplaced during the Jurassic to Cretaceous Daebo orogeny.     

Oyster and Macroalgae Bioindicators Detect Elevated δ<Superscript>15</Superscript>N in Maryland’s Coastal Bays

Nitrogen loading from anthropogenic sources, including fertilizer, manure, and sewage effluents, has been linked with declining water quality in coastal lagoons worldwide. Freshwater inputs to mid-Atlantic coastal lagoons of the USA are from terrestrially influenced sources: groundwater and overland flow via streams and agricultural ditches, with occasional precipitation events. Stable nitrogen isotopes ratios (δ¹⁵N) in bioindicator species combined with conventional water quality monitoring were used to assess nitrogen sources and provide insights into their origins. Water quality data revealed that nutrients derived from terrestrial sources increased after precipitation events. Tissues from two bioindicator species, a macroalgae (Gracilaria sp.) and the eastern oyster (Crassostrea virginica) were analyzed for δ¹⁵N to determine spatial and temporal patterns of nitrogen sources. A broad-scale survey assessment of deployed macroalgae (June 2004) detected regions of elevated δ¹⁵N. Macroalgal δ¹⁵N (7.33 ± 1.15‰ in May 2006 and 6.76 ± 1.15‰ in July 2006) responded quickly to sustained June 2006 nutrient pulse, but did not detect spatial patterns at the fine scale. Oyster δ¹⁵N (8.51 ± 0.89‰) responded slowly over longer time periods and exhibited a slight gradient at the finer spatial scale. Overall, elevated δ¹⁵N values in macroalgae and oysters were used to infer that human and animal wastes were important nitrogen sources in some areas of Maryland’s coastal bays. Different nitrogen integration periods across multiple organisms may be used to indicate nitrogen sources at various spatial and temporal scales, which will help focus nutrient management.     

Oxygen and hydrogen isotopes for the characteristics of groundwater recharge: a case study from the Chih-Pen Creek basin,Taiwan

Assessing the seasonal variation of groundwater recharge is important for effective management of groundwater resources. Stable isotopes of oxygen and hydrogen were used to estimate the sources of groundwater and seasonal contributions of precipitation to groundwater recharge in Chih-Pen Creek basin of eastern Taiwan. Based on the isotopes of precipitation (n = 177), two different local meteoric water regression lines (LMWL) can be obtained for the different seasons: δD = 8.06¹⁸O + 10.08 for wet season precipitation (May through October) and δD = 8.65δ¹⁸O + 17.09 for dry season precipitation (November through April). The slope and intercept of regression line for wet season precipitation are virtually identical to the global meteoric water line (GMWL) of Craig (1961). In contrast to during dry season precipitation due to evaporation effect the intercept of 17.09 is much higher than of the GMWL of 10. The results show the stable isotopes compositions of precipitation decrease with increasing rainfall amount and air temperature, due to the amount effect of precipitation is pronounced. The amount effect is clearly but do not show the temperature effect from January to December 2007. Using a mass-balance equation, a comparison of deuterium excess or d values of precipitation and groundwater indicates the groundwater consist of 76% wet season precipitation and 24% dry season precipitation, representing a distinct seasonal variation of groundwater recharge in study area. About 79% of the groundwater is recharged from the river water of the mountain watershed and 21% is from the rain that falls on the basin.     

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996     

Recharge source and hydrogeochemical evolution of shallow groundwater in a complex alluvial fan system,southwest of North China Plain

Many cities around the world are developed at alluvial fans. With economic and industrial development and increase in population, quality and quantity of groundwater are often damaged by over-exploitation in these areas. In order to realistically assess these groundwater resources and their sustainability, it is vital to understand the recharge sources and hydrogeochemical evolution of groundwater in alluvial fans. In March 2006, groundwater and surface water were sampled for major element analysis and stable isotope (oxygen-18 and deuterium) compositions in Xinxiang, which is located at a complex alluvial fan system composed of a mountainous area, Taihang Mt. alluvial fan and Yellow River alluvial fan. In the Taihang mountainous area, the groundwater was recharged by precipitation and was characterized by Ca–HCO₃ type water with depleted δ¹⁸O and δD (mean value of −8.8‰ δ¹⁸O). Along the flow path from the mountainous area to Taihang Mt. alluvial fan, the groundwater became geochemically complex (Ca–Na–Mg–HCO₃–Cl–SO₄ type), and heavier δ¹⁸O and δD were observed (around −8‰ δ¹⁸O). Before the surface water with mean δ¹⁸O of −8.7‰ recharged to groundwater, it underwent isotopic enrichment in Taihang Mt. alluvial fan. Chemical mixture and ion exchange are expected to be responsible for the chemical evolution of groundwater in Yellow River alluvial fan. Transferred water from the Yellow River is the main source of the groundwater in the Yellow River alluvial fan in the south of the study area, and stable isotopic compositions of the groundwater (mean value of −8.8‰ δ¹⁸O) were similar to those of transferred water (−8.9‰), increasing from the southern boundary of the study area to the distal end of the fan. The groundwater underwent chemical evolution from Ca–HCO₃, Na–HCO₃, to Na–SO₄. A conceptual model, integrating stiff diagrams, is used to describe the spatial variation of recharge sources, chemical evolution, and groundwater flow paths in the complex alluvial fan aquifer system.     

Origin of the Zálesí U–Ni–Co–As–Ag/Bi deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Zálesí vein-type deposit is hosted by Early Paleozoic high-grade metamorphic rocks on the northern margin of the Bohemian Massif. The mineralization is composed of three main stages: uraninite, arsenide, and sulfide. The mineral assemblages formed at low temperatures (~80 to 130°C, locally even lower) and low pressures (<100 bars). The salinity of the aqueous hydrothermal fluids (0 to 27 wt.% salts) and their chemical composition vary significantly. Early fluids of the oldest uraninite stage contain a small admixture of a clathrate-forming gas, possibly CO₂. Salinity correlates with oxygen isotope signature of the fluid and suggests mixing of brines [δ ¹⁸O around +2‰ relative to standard mean ocean water (SMOW)] with meteoric waters (δ ¹⁸O around −4‰ SMOW). The fluid is characterized by highly variable halogen ratios (molar Br/Cl = 0.8 × 10⁻³ to 5.3 × 10⁻³; molar I/Cl = 5.7 × 10⁻⁶ to 891 × 10⁻⁶) indicating a dominantly external origin for the brines, i.e., from evaporated seawater, which mixed with iodine-enriched halite dissolution brine. The cationic composition of these fluids indicates extensive interaction of the initial brines with their country rocks, likely associated with leaching of sulfur, carbon, and metals. The brines possibly originated from Permian–Triassic evaporites in the neighboring Polish Basin, infiltrated into the basement during post-Variscan extension and were finally expelled along faults giving rise to the vein-type mineralization. Cenozoic reactivation by low-salinity, low-δ ¹⁸O (around −10‰ SMOW) fluids of mainly meteoric origin resulted in partial replacement of primary uraninite by coffinite-like mineral aggregates.     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

Hydrogeochemical and Stable Isotope Characteristics of the River Idrijca (Slovenia), the Boundary Watershed Between the Adriatic and Black Seas

The hydrogeochemical and isotope characteristics of the River Idrijca, Slovenia, where the world’s second largest mercury (Hg) mine is located, were investigated. The River Idrijca, a typical steep mountain river, has an HCO₃ ⁻–Ca²⁺–Mg²⁺ chemical composition. Its Ca²⁺/Mg²⁺ molar ratio indicates that dolomite weathering prevails in the watershed. The River Idrijca and its tributaries are oversaturated with respect to calcite and dolomite. The pCO₂ pressure is up to 13 times over atmospheric pressure and represents a source of CO₂ to the atmosphere. δ¹⁸O values in river water indicate primary control from precipitation and enrichment of the heavy oxygen isotope of infiltrating water recharging the River Idrijca from its slopes. The δ¹³C_DIC values range from −10.8 to −6.6‰ and are controlled by biogeochemical processes in terrestrial environments and in the stream: (1) exchange with atmospheric CO₂, (2) degradation of organic matter, (3) dissolution of carbonates, and (4) tributaries. The contributions of these inputs were calculated according to steady state equations and are estimated to be—11%:19%:30%:61% in the autumn and 0%:26%:39%:35% in the spring sampling seasons.     

Volcanogenic-related origin of sulfide-rich quartz veins: evidence from O and S isotopes at the Géant Dormant gold mine, Abitibi belt, Canada

The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ¹⁸O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ¹⁸O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ¹⁸O value of 4.7‰ calculated at 275 °C. The δ³⁴S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ¹⁸O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ¹⁸O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999     

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     

A fluid inclusion and isotopic study of an intrusion-related gold deposit (IRGD) setting in the 380 Ma South Mountain Batholith,Nova Scotia,Canada: evidence for multiple fluid reservoirs

A set of sheeted quartz veins cutting 380 Ma monzogranite at Sandwich Point, Nova Scotia, Canada, provide an opportunity to address issues regarding fluid reservoirs and genesis of intrusion-related gold deposits. The quartz veins, locally with arsenopyrite (≤5%) and elevated Au–(Bi–Sb–Cu–Zn), occur within the reduced South Mountain Batholith, which also has other zones of anomalous gold enrichment. The host granite intruded (P = 3.5 kbars) Lower Paleozoic metaturbiditic rocks of the Meguma Supergroup, well known for orogenic vein gold mineralization. Relevant field observations include the following: (1) the granite contains pegmatite segregations and is cut by aplitic dykes and zones (≤1–2 m) of spaced fracture cleavage; (2) sheeted veins containing coarse, comb-textured quartz extend into a pegmatite zone; (3) arsenopyrite-bearing greisens dominated by F-rich muscovite occur adjacent the quartz veins; and (4) vein and greisen formation is consistent with Riedel shear geometry. Although these features suggest a magmatic origin for the vein-forming fluids, geochemical studies indicate a more complex origin. Vein quartz contains two types of aqueous fluid inclusion assemblages (FIA). Type 1 is a low-salinity (≤3 wt.% equivalent NaCl) with minor CO₂ (≤2 mol%) and has T _h = 280–340°C. In contrast, type 2 is a high-salinity (20–25 wt.% equivalent NaCl), Ca-rich fluid with T _h = 160–200°C. Pressure-corrected fluid inclusion data reflect expulsion of a magmatic fluid near the granite solidus (650°C) that cooled and mixed with a lower temperature (400°C), wall rock equilibrated, Ca-rich fluid. Evidence for fluid unmixing, an important process in some intrusion-related gold deposit settings, is lacking. Stable isotopic (O, D, S) analyses for quartz, muscovite and arsenopyrite samples from vein and greisens indicate the following: (1) δ¹⁸O_qtz = +11.7‰ to 17.8‰ and δ¹⁸O_musc = +10.7‰ to +11.2‰; (2) δD_musc = −44‰ to−54‰; and (3) δ³⁴S_aspy = +7.8‰ to +10.3‰. These data are interpreted, in conjunction with fluid inclusion data, to reflect contamination of a magmatic-derived fluid (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  ≤ +10‰) by an external fluid (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  ≥ +15‰), the latter having equilibrated with the surrounding metasedimentary rocks. The δ³⁴S data are inconsistent with a direct igneous source based on other studies for the host intrusion (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  = +5‰) and are, instead, consistent with an external reservoir for sulphur based on δ³⁴S_H2S data for the surrounding metasedimentary rocks. Divergent fluid reservoirs are also supported by analyses of Pb isotopes for pegmatitic K-feldspar and vein arsenopyrite. Collectively the data indicate that the vein- and greisen-forming fluids had a complex origin and reflect both magmatic and non-magmatic reservoirs. Thus, although the geological setting suggests a magmatic origin, the geochemical data indicate involvement of multiple reservoirs. These results suggest multiple reservoirs for this intrusion-related gold deposit setting and caution against interpreting the genesis of intrusion-related gold deposit mineralization in somewhat analogous settings based on a limited geochemical data set.