Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Oxygen isotope study of a Precambrian banded iron-formation,Hamersley Range,Western Australia

Oxygen isotope ratios were determined for quartz, magnetite, ankerite, siderite, riebeckite, hematite and talc in samples of banded iron-formation from the Dales Gorge Member of the Brockman Iron Formation and for quartz, dolomite and calcite in samples of the Wittenoom Dolomite and Duck Creek Dolomite Formations, all from the Hamersley Range area of Western Australia. Additionally, in order to interpret the measured isotope ratios, isotopic fractionations for oxygen between quartz, siderite and magnetite and between these minerals and water as a function of temperature were calculated, using a combination of spectroscopic and thermodynamic data and constraints set by experimental determinations of the fractionations.The Dales Gorge Member was found to have undergone isotopic exchange between minerals at a temperature estimated on the basis of the isotopic fractionations to be above 270°C and probably less than 310°C, during burial metamorphism. At these temperatures quartz and the carbonates were almost completely equilibrated with one another, while hematite apparently underwent negligible exchange. Magnetite may have undergone exchange in some samples but not others, as a result of permeability variations, or it may have been as resistant to exchange as hematite. Riebeckite, and probably talc as well, were also subject to exchange, but to a lesser degree or on a smaller scale than quartz and the carbonates. Hematite formed at temperatures of 140°C or below. Magnetite appears to have formed at temperatures above 140°C, and possibly over a range of temperatures between about 180 and 300°C.The Wittenoom Dolomite and Duck Creek Dolomite samples show apparent lack of equilibrium, due to incomplete exchange or to retrograde effects. A chert from the Wittenoom Dolomite, along with two samples from the Marra Mamba Iron Formation, with δ¹⁸O values of + 24%. can be considered to set a lower limit of about ?11%. on the δ¹⁸O value of the ocean 2.2 × 10⁹ yr ago. Internal fractionations in the Wittenoom Dolomite chert sample may be interpreted as yielding an upper limit on this oceanic δ¹⁸O value of ? 3.5%.     

Isotopic evidence of the origin of mineralized waters from the Central Carpathian Synclinorium,SE Poland

Stable isotopes of hydrogen and oxygen were determined in 45 samples of water (27 samples of oil-associated waters, 17 samples of mineral waters used by spas, 1 sample of surface river water) from the Central Carpathian Synclinorium, covering a stratigraphic range of flysch sediments from Upper Cretaceous to Oligocene. Moreover, oxygen isotope compositions of authigenic calcite (vein and cement) from core samples of four boreholes were made to evaluate isotopic equilibrium between waters and diagenetic carbonates as a function of temperature. The saline and brackish waters (TDS from1 g/l to 48.9 g/l) considered here, generally belong to four hydrogeochemical classes: Na-Cl, Cl-HCO₃-Na, HCO₃-Cl-Na and HCO₃-Na. Their isotopic composition causes them to fall to the right of Global Meteoric Water Line (GMWL) showing enrichment in ¹⁸O and ²H. On the other hand, relative to Standard Mean Ocean Water (SMOW) they are depleted in ²H and both depleted and enriched in ¹⁸O. The observed isotopic composition can be explained by the three-component mixing of surface water, diagenetically modified sea water (kind of connate water) and metamorphic water. The mixing is accompanied by an exchange of oxygen isotopes between water and carbonate cements causes ¹⁸O enrichment of interstitial waters. The contribution of isotopic exchange between water and clay minerals in shales was evaluated only theoretically basing of the literature.     

Carbon and oxygen isotope zoning around Carlin-type gold deposits: a reconnaissance survey at Twin Creeks, Nevada

This study was undertaken to determine whether wallrocks around the Twin Creeks Carlin-type gold deposits exhibit oxygen isotope haloes similar to those found around other types of hydrothermal deposits. Mineralization at Twin Creeks is hosted by Ordovician Sequence shales containing some carbonate minerals and by Pennsylvanian–Permian Etchart Formation limestone. Analysis of orthophosphate-soluble carbonate from these rocks shows that oxygen isotope haloes are detectable in Ordovician Sequence shales but not in Etchart Formation limestone. The soluble fraction of Ordovician Sequence shales at Twin Creeks has δ¹⁸O values of 12 to 24‰ and δ¹³C values of 0 to −10‰. Most samples fall along a poorly defined trend that extends from δ¹⁸O of about 24‰ and δ¹³C values of about 0, which are typical of unaltered limestones, toward lower values for both isotope systems, which are typical of rocks that have undergone alteration by hydrothermal fluids. Plots of these values along two sections through the ore body show that δ¹⁸O values of wallrocks are lowest in the ore zone and increase outward, forming a halo several hundred meters in size. In the same plots, δ¹³C values of the wallrocks do not show systematic spatial variations. The soluble fraction of Etchart Formation limestones at Twin Creeks have δ¹⁸O values of 25 to 5‰ and δ¹³C values of 4 to −10‰, but do not show any systematic spatial variation relative to mineralization at the scale of our samples. Failure of the Etchart Formation samples to show detectable haloes is probably related to deposition of post-ore carbonate minerals or lower ore fluid : rock ratios. Material balance calculations used to model the isotopic composition of average Ordovician Sequence shales indicate that changes in temperature and water : rock ratio were probably not sufficient to account for the wide range of isotope compositions observed in these rocks. The most likely additional factor contributing to this range of values was a change in the composition of the altering fluid, probably by mixing of the ore fluid with surrounding meteoric water. These results suggest that Carlin-type gold deposits are surrounded by haloes of low δ¹⁸O values, but that detection of these haloes could be complicated by local compositional variations and post-ore modification of the wallrocks.     

Evaluation of bulk carbonate δ13C data from Triassic hemipelagites and the initial composition of carbonate mud

Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ¹³C and δ¹⁸O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ¹³C and δ¹⁸O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ¹³C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ¹³C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.     

Experimentally-controlled carbon and oxygen isotope exchange between bioapatites and water under inorganic and microbially-mediated conditions

Modern bone and enamel powders have reacted at 301 K with ¹³C- and ¹⁸O-labelled waters under inorganic and microbial conditions. The aim of the study is to investigate the resistance of stable isotope compositions of bioapatite carbonate (δ¹³C, δ¹⁸Oc) and phosphate (δ¹⁸Op) to isotopic alteration during early diagenesis. Rapid and significant carbon and oxygen isotope changes were observed in the carbonate and phosphate fractions of bone apatite before any detectable change occurred in the crystallinity or organic matter content. These observations indicate that chemical alterations of bone apatite are likely to start within days of death. Enamel crystallites are much more resistant than bone crystallites, but are not exempt of alteration. Non removable carbon and oxygen isotope enrichments were measured in the carbonate phase of bone (50-90%) and enamel (40%) after the acetic acid treatment. This result indicates that a significant part of ¹³C and ¹⁸O-labelled coming from the aqueous fluid has been durably incorporated into the apatite structure, probably through isotopic exchange or secondary carbonate apatite precipitation. As a result, acetic acid pre-treatments that are currently used to remove exogenous material by selective dissolution, are not adequate to restore pristine δ¹³C and δ¹⁸Oc values of fossil apatites. Under inorganic conditions, kinetics of oxygen isotope exchange are 10 times faster in carbonate than in phosphate. On the opposite, during biologically-mediated reactions, the kinetics of oxygen isotope exchange between phosphate and water is, at least, from 2 to 15 times faster than between carbonate and water. Enamel is a more suitable material than bone for paleoenvironmental or paleoclimatical reconstructions, but interpretations of δ¹⁸Op or δ¹³C values must be restricted to specimens for which no or very limited trace of microbial activity can be detected.     

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

Isotopic variations of oxygen and hydrogen in groundwater of carbonate aquifer in an arid environment

The stable isotopic characteristics were used together with the total chloride to assess changes in groundwater from recharge zones into the carbonate aquifer in an arid environment. The aquifer under study represents a major source of groundwater and thermal springs in Al-Ain city, which are located at the northern part of Jabal Hafit in the United Arab Emirates (UAE). The relationship between oxygen and hydrogen isotopic composition of groundwater is established and is described by δD?=?2.2δ¹⁸O???9.96. The lower slope and y-intercept of groundwater samples relative to the local meteoric waterline suggests that the isotopic enrichment is due to the evaporation of shallow groundwater after recharge occurs. The majority of the shallow groundwater samples have a negative deuterium excess (d-excess) which might be ascribed to high a degree of evaporation, while most of the groundwater samples from deep wells, have a positive value of d-excess which may be related to a low degree of evaporation. The δ¹⁸O values of the thermal waters suggest enrichment towards δ¹⁸O of the carbonate rocks because of the exchange with oxygen at higher temperatures. A possible mixing between thermal or hot water and shallow groundwater is evident in some samples as reflected by δD vs. Cl and d-excess vs. δ¹⁸O plots.     

A strontium isotopic study of formation waters from the Illinois basin, U.S.A.

The isotopic composition of Sr has been measured in 73 formation-water samples from Paleozoic strata in the Illinois basin; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7079 to 0.7108. With the exception of four samples, the waters are more radiogenic than corresponding Paleozoic sea-water values. The relatively narrow range of slightly elevated ⁸⁷Sr/⁸⁶Sr rations is uniformly distributed in waters throughout the stratigraphic column and in Silurian waters across the basin. Isotopic analyses of core samples from reservoir rocks show an absence of water-rock Sr isotopic equilibration. Basin lithology and analyses of detrital rock units indicate that clay minerals in shales and in quartz sandstone matrices represent the only significant source of radiogenic Sr for the waters. Silurian and Devonian water show a two-component mixing relation which suggests that they comprise a single hydrogeological system that evolved when radiogenic water from New Albany shales entered Silurian-Devonian carbonate rocks and mixed with marine interstitial water. Regional migration of the waters and associated petroleum within the Silurian-Devonian strata, proposed in other studies, is consistent with the Sr isotopic data. Under favorable circumstances subsurface waters are capable of retaining a Sr isotopic recor of their evolution.     

Shoreline tufa and tufaglomerate from Pleistocene Lake Bonneville,Utah, USA: stable isotopic and mineralogical records of lake conditions,processes, and climate

Shoreline carbonate deposits of Pleistocene Lake Bonneville record the conditions and processes within the lake, including the evaporative balance as well as vertical and lateral chemical and isotopic gradients. Tufas (swash‐zone) and tufaglomerates (cemented, subaqueous colluvium or beachrock) on multiple, well‐developed shorelines near the Silver Island Range, Utah, also present an opportunity to examine physicochemical lake processes through time. Three shorelines are represented by carbonate deposits, including the 23–20 ka Stansbury stage, 15–14.5 ka Bonneville stage, and 14.5–14 ka Provo stage. Mean δ¹⁸O_VSMOW values of all three shorelines are statistically indistinguishable ( ～ 27 ± 1‰), when a few Bonneville samples of unusual composition are neglected. However, differences in primary carbonate mineralogy indicate that the correspondence is an artefact of the different fractionation factors between calcite or aragonite and water. Second, in order to sustain a much smaller, shallower lake during the colder Stansbury stage, the climate must have also been relatively dry. Third, δ¹⁸O values in tufa are higher than tufaglomerate by ～ 0.5‰, consistent with greater evaporative enrichment of lake water in the swash zone. Fourth, mean δ¹³C values for the Provo, Stansbury and Bonneville shorelines (4.4, 5.0 and 5.2‰, respectively) show that carbon species were dominated by atmospheric exchange, with the variations produced by differences in the oxidation of organic matter. Comparisons of shoreline carbonates with deep‐lake marls of the same approximate age indicate that shoreline carbonate was much higher in δ¹³C and δ¹⁸O values (both ～ 2.5‰) during Bonneville time, whereas isotopic differences were minor (both ～ 1‰) in Stansbury time. In particular, the Bonneville stage may have sustained large vertical or lateral isotopic gradients due to evaporative enrichment effects on δ¹⁸O values. In contrast, the lake during the much shallower Stansbury stage may have been well mixed. Differences in the primary mineralogy (Stansbury and Bonneville, aragonite > calcite; Provo, calcite > aragonite) reflect profound differences in lake chemistry in terms of open versus closed‐basin lakes. The establishment of a continuous outlet during Provo time probably reduced the Mg²⁺/Ca²⁺ ratio of lake water. Curiously, regardless of primary mineralogy, tufaglomerate cements are enriched in Na⁺ and Cl^? and depleted in Mg²⁺ relative to capping tufa of the same age. This probably reflects vital or kinetic effects in the swash zone (tufa). We suspect that ‘abiotic’ effects may have been important in the dark pore space of developing tufaglomerate, where the absence of light suppressed photosynthesis. Copyright © 2005 John Wiley & Sons, Ltd.     

Evaluation of oxygen isotopes in carbonate as an indicator of lake evolution in arid areas: The modern Qinghai Lake, Qinghai–Tibet Plateau

The oxygen isotopic composition of carbonate in lakes has been used as a useful indicator in Palaeolimnological research, and has made some important contributions to our understanding of lacustrine systems. For modern lakes in arid or cold areas, however, there are few data available to test the effect of lake salinity and temperature on the oxygen isotopic composition of various carbonate sources such as ostracod, bulk carbonate, and fine-grained carbonate (< 60 μm). Here we examined the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonates, as well as that of coexisting water from Lake Qinghai and the smaller surrounding lakes and ponds on the Qinghai–Tibet Plateau. Our investigation highlights three key effects. First, the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonate in the lakes and ponds shows a clear response to lake water δ¹⁸O values, and these vary with water salinity. The relationship between lake water δ¹⁸O and salinity is not only dominated by the evaporation/freshwater input ratios, but is also controlled by the distance to the mouth of the major rivers supplying to the lake. Second, the ostracod, bulk carbonate, and fine-grained carbonate show similar isotopic change trends in the study area, and oxygen isotopic differences between ostracods and authigenic carbonate may be explained by the different water temperatures and very small ‘vital offsets’ of ostracods. Finally, the effect of water depth on temperature leads to increasing δ¹⁸O values in carbonates as water depth increases, both in benthic ostracods living on the lake bottom, as well as in bulk carbonate precipitated at the water surface.For arid, high-altitude Lake Qinghai, our results suggest that variations in the δ¹⁸O values of carbonate in Lake Qinghai are mainly controlled by the oxygen-isotope ratio of the lake water changing with water salinity. As a secondary effect, increasing water depth leads to cooler bottom and surface water, which may result in more positive δ¹⁸O values of ostracod and bulk carbonate.     

Diagenetic evolution of the Carnian Wetterstein platforms of the Eastern Alps

The carbonate platforms of the Wetterstein Formation of the Eastern Alps (Drau Range and Northern Calcareous Alps) show a distinct facies zonation of reefs and lagoons. While some lagoonal areas were episodically emerged and formed lagoonal islands, others remained permanently flooded. The scale of near surface, meteoric or marine diagenesis was related to this lagoonal topography. At shallow burial depth, cementation was dominated by altered marine solutions, which additionally caused recrystallization of metastable constituents of the sediment and earlier marine cements (high magnesian calcite, aragonite) connected with a carbon and oxygen isotopic change to more negative values. Deeper burial cementation shows a succession with two types of saddle dolomite and three types of blocky calcite. Carbon and oxygen isotopic values of these cements show a trend towards more negative values from the first to the last generation, in the following succession: clear saddle dolomite—zoned blocky calcite—cloudy saddle dolomite—post-corrosion blocky calcite—replacive blocky calcite. Fluid inclusion studies of the carbonate cements are interpreted to indicate a deeper burial temperature development that first increases from 175 to 317°C, followed by a temperature decrease to 163–260°C, and subsequent increase up to 316°C, whereby the samples of the Drau Range always show the lowest values. Calculations of the isotopic composition of the water, from which the carbonate cements were precipitated, yielded positive δ¹⁸O values from 6.66 to 17.81%o (SMOW), which are characteristic for formation and/or metamorphic waters. Also, the isotopic compositions of the palaeofluids probably changed during deeper burial diagenesis, following the temperature development.     

Oxygen and carbon isotope measurements of land snail shell carbonate

δ¹³C and δ¹⁸O analyses have been performed on the aragonite shells of a variety of modern land snails from a number of different geographic and climatic locales. The δ¹⁸O values of the waters assumed to be in isotopic equilibrium with the shell carbonate were calculated. These calculated δ¹⁸O values are more positive than the δ¹⁸O values of the average meteoric waters in the locales in which the snails lived. The ¹⁸O enrichment appears to be linearly related to the reciprocal of the local relative humidity, which is consistent with the notion that these ambient waters have undergone isotopic steady-state evaporation. Measurements of the δ¹⁸O values of ancient land snail shells from the excavation of Sudden Shelter (42SV6) at Ivie Creek, Utah, suggest that the climate at this site was probably warmer and/or drier around 7100–7800 BP than at present.     

Strontium and oxygen isotopic systems in waters of mud volcanoes of the Taman Peninsula

Ten of eleven analyzed water samples from mud volcanoes of the Taman Peninsula are characterized by ⁸⁷Sr/⁸⁶Sr ratio within 0.70734–0.70957, which overlaps the values typical of the Mesozoic and Cenozoic sedimentary carbonates, but sharply differs from the value in the clayey sediments of the Maikop Group (0.7157 ± 0.0022). These data indicate that the strontium isotopic composition is mainly defined by carbonate reservoirs, with relatively little effect of elision solutions, input of which is noticeable only in the water of Gladkovsky Volcano (⁸⁷Sr/⁸⁶Sr = 0.71076). The high δ¹⁸O in mud volcanic waters (up to 14.2‰) can also be attributed to ionic exchange with sedimentary carbonates at temperatures around 150°C.     

Ion microprobe analysis of graphite from ca. 3.8 Ga metasediments, Isua supracrustal belt, West Greenland: Relationship between metamorphism and carbon isotopic composition

In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ¹³C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ¹³C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ¹³C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ¹³C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively ¹³C-depleted graphite indicates that the regional metamorphism increased the δ¹³C values of the Isua graphite. This is consistent with the regional trend of ¹³C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused ¹³C-enrichment of Isua graphite. The δ¹³C values of graphite reported here (δ¹³C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ¹³C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the ¹³C-enrichment of Isua graphite, previously reported large ¹³C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).     

Geochemistry and potential use of groundwater in the Rocca Busambra area (Sicily, Italy)

In the Rocca Busambra area (mid-west Sicily, Italy), from November 1999 to July 2002, 23 water points including wells and springs were sampled and studied for their chemical and isotopic compositions. Two rain gauges were also installed at different altitudes, and rainwater was collected monthly to determine the isotopic composition. The obtained results revealed the Rocca Busambra carbonate complex as being the main recharge area on account of its high permeability value. From a chemical view point, two main groups of water can be distinguished: calcium–magnesium–bicarbonate-type and calcium–magnesium–chloride–sulphate-type waters. The first group reflects the dissolution of the carbonate rocks; the second group probably originates from circulation within flyschoid sediments. Three water wells differ from the other samples due to their relatively high Na and K content, which probably is to be referred to a marked interaction with the “Calcareniti di Corleone” formation, which is rich in glauconite [(K, Na)(Fe³⁺, Al, Mg)₂(Si, Al)₄O₁₀(OH)₂]. In accordance with WHO guidelines for drinking water (2004), almost all the samples collected can be considered drinkable, with the exception of four of them, whose NO₃ ⁻, F⁻ and Na⁺ contents exceed the limits. On the contrary, the sampled groundwater studied is basically suitable for irrigation.     

Zoned calcites in Jurassic ammonite chambers: trace elements, isotopes and neomorphic origin

Zoned calcites were found in the phragmacone chambers of three Sonniniid ammonites from marine Middle Jurassic sandstones (Isle of Skye, U.K.). Each ammonite has a unique sequence of up to nine zones of calcite which fill or partially fill the chambers. Zones are defined by changes in the density of minute opaque inclusions and variation in trace-element composition. Proximal (early) calcites have undulose extinction and some exhibit the specific fabrics of fascicular-optic and radiaxial fibrous calcites. Microdolomite inclusions are found in one specimen. Early calcites, interpreted as replacements after a single isopachous fringe of acicular carbonate (probably high magnesium calcite), are succeeded by blocky ferroan calcite cement. In one specimen there are two distinct generations of calcite, in the others there is a continuous mosaic incorporating both early calcites and late cement. Isotopic composition of the early calcite zones demonstrates the initial importance of organic derived carbon (δ¹³C =— 26‰, δ¹⁸O ‰ O). Further cementation and mineralogical stabilization took place at increased temperatures and probably after modification of the pore water isotopic composition (calcites with δ¹³C =— O‰, δ¹⁸O～— 10‰). The distinctive fabrics and zonal patterns probably developed during the replacement of the precursor cement and are not primary growth features. Reversals in isotopic and trace element trends are believed to be related to the rate of neomorphic crystal growth and hence to the degree of exchange with external pore waters. Further increase in temperature, probably during Tertiary igneous activity, gave rise to the extremely light δ¹⁸O values of the late cements in the ammonite which had previously had least contact with external waters (cements with δ¹³C ～ O, δ¹⁸O ～— 20‰).     

On the stable carbon and oxygen isotopic composition of some shallow water,ahermatypic, scleractinian coral skeletons

The δC¹³ and δO¹⁸ values of skeletons of shallow water, ahermatypic scleractinian corals from Jamaica show an excellent correlation over a wide range of isotopic composition. Within individual specimens there are large differences in the isotopic composition of separate skeletal elements. Some of these ahermatypes are enriched in O¹⁸ relative to equilibrium precipitates of calcium carbonate from Jamaican sea water. Therefore our data do not support a two-reservoir mixing model for calcification if one of these reservoirs consists of dissolved marine (inorganic) bicarbonate. As some of these ahermatypic species are enriched in both C¹³ and O¹⁸ relative to hermatypic corals from the same reefs, calcification models based on withdrawal of metabolic CO₂ by photosynthesizing zooxanthellae must also be modified.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Oxygen and hydrogen isotopic studies of ore deposition and metamorphism at the Raul mine,Peru

The volcano-sedimentary sequence at the Raul mine, central Peru, consists of andesitic volcanics, graywackes, and siltstones, and has been metamorphosed to the upper greenschist-lower amphibolite facies at temperatures of 400–500°C. Isotopic data (O and H) have been collected from: (a) quartz and magnetite from stratiform ores, (b) amphiboles from amphibolite units that host stratiform ores, (c) calcite from late veins, (d) detrital quartz from graywackes, and (e) whole rocks.Interunit differences in quartz and magnetite δ¹⁸O values suggest that these minerals have resisted isotopic exchange during metamorphism, and that quartz-magnetite isotopic temperatures (380–414°C) represent primary formational temperatures. Calculated δ¹⁸O values of water in equilibrium with quartz and magnetite range from 9.1 to 12.6%..Amphibole δ¹⁸O and δD values show no interunit differences and suggest that the amphiboles have exchanged isotopes with a large metamorphic fluid reservoir. Calculated δ¹⁸O_H2O and δD_H2O values range from 8 to 12%. and ?3 to +42%., respectively.δ¹⁸O_H2O values calculated from δ¹⁸O calcite and fluid inclusion filling temperatures range from 7.5 to 10%.. Water extracted from fluid inclusions in calcite has a δD value of ?20%..δ¹⁸O values of metamorphosed graywackes and volcanic sediments are not atypical, but andesitic lavas are ¹⁸O-rich (8–10%.) compared to normal andesites.Waters involved in ore deposition, metamorphism, and late vein formation at Raul are all thought to have a common source, principally seawater. The δ¹⁸O_H2O and δD_H2O values could be produced by evaporation of seawater, shale ultrafiltration, and isotopic exchange with host rocks during deep circulation through the volcano-sedimentary pile.A model is proposed whereby coastal ocean water is restricted from the open sea by volcanic island arcs, and subsequently undergoes evaporation. Circulation of this water is initiated by heat associated with seafloor volcanism. ¹⁸O-enrichment in andesites may be produced by isotopic exchange with high ¹⁸O waters at elevated temperatures and sufficiently high water/rock ratios.