Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

The oxygen isotopic composition of phosphate as an effective tracer for phosphate sources in Hongfeng Lake

In order to characterize the oxygen isotopic composition of internal phosphate and explore the possibility of using these data to identify phosphate sources, we measured oxygen isotopic compositions of phosphate (δ¹⁸O_p) in sediment pore water in Hongfeng Lake, a typical deep-water lake in a mountainous area. These data, in combination with δ¹⁸O_p in surface water samples and water column samples, were successfully used to identify phosphate sources. The δ¹⁸O_p value of sediment pore water ranged from 15.2‰ to 15.8‰, with an average value of 15.5‰—the δ¹⁸O_p value of internal phosphate. The δ¹⁸O_p values decreased gradually through the water column from 19.4‰ in surface water to 16.4‰ in deeper water, implying that internal phosphate had more negative δ¹⁸O_p values than external phosphate. This finding was substantiated by horizontal variations in δ¹⁸O_P values, which decreased with increasing distance from inflowing rivers. All collected evidence suggests that external and internal phosphate have distinctly different isotopic signatures and that these signatures have not been considerably altered by biological mediation in Hongfeng Lake. Therefore, δ¹⁸O_P can be used to distinguish phosphate sources. A two-endmember mixing model showed that internal phosphate had an average contribution of 40%, highlighting the influence of internal phosphorus loading on aqueous phosphate and eutrophication. This study illustrates the need to reduce the internal phosphorus load from sediment and provides guidance for nutrient management and in-lake restoration treatment in Hongfeng Lake. The data presented here are limited, but serve to highlight the great potential of δ¹⁸O_p as an effective tracer for identifying phosphate sources. Systematic investigations of the oxygen isotopic compositions of external phosphate, internal phosphate, and phosphate through the water column, in combination with in-lake P biogeochemical cycle study, would be desirable in further research.     

The carbon isotopic composition of diamonds: relationship to diamond shape,color, occurrence and vapor composition

Three hundred and thirty new ¹³C analyses of diamonds are presented, indicating, in conjunction with earlier published work, a range of about 30%. in the carbon isotopic composition of diamonds. The frequency distribution of diamond δ¹³C analyses shows a very pronounced mode at ?5 to ?6%.vs PDB, a large negative skewness, and a sharp boundary at about ?1%.. Analyses of diamonds from the Premier and Dan Carl mines, South Africa, demonstrate that: (1) differences in ¹³C content that can be related to diamond color and shape are smaller than 1%.; (2) the mean ¹³C content of kimberlite carbonates is 1–2%. lower than that of associated diamonds; (3) significant differences in ¹³C content exist between the mean isotopic compositions of diamonds from these two pipes; (4) the variability in δ¹³C differs from one mine to the other.Computations were carried out evaluating the effect on the ¹³C content of diamonds of: (i) various precipitation processes; (ii) the abundance of the species H₂, H₂O, CH₄, CO, CO₂ and O₂ in the vapor; (iii) the initial isotopic composition variability of the source carbon; (iv) variations of the carbon isotope effects resulting from changes in pressure and temperature and (v) reservoir effects (Rayleigh fractionation). Fifty-eight genetic models were investigated for compatibility with the ¹³C distribution in diamonds and associated carbonate. The modeling does not permit an unambiguous answer to the question whether or not a vapor participated in diamond formation, although the presence of methane during diamond formation is compatible with the carbon isotopic composition data, possible oxygen fugacities in the mantle and with the composition of gases liberated from diamonds. In all probability carbon isotope effects in the diamond formation process were small, and the very large range in δ¹³C observed was inherited from the source carbon.     

The isotopic composition of carbonatite and kimberlite carbonates and their bearing on the isotopic composition of deep-seated carbon

New carbon and oxygen isotopic compositions of carbonates from 14 carbonatite and 11 kimberlite occurrences are reported. A review of the available data on the carbon isotopic composition ranges of carbonatite and kimberlite carbonates shows that they are similar and overlap that of diamonds. The mean carbon isotopic composition of carbonates from 22 selected carbonatite complexes (?5.1%., s = ±l.4%.vsPDB) is indistinguishable from that of 13 kimberlite pipes (?4.7%. s = ±1.2%.) as well as that of 60 individual diamond analyses (?5.8%., s = 1.8%.). The oxygen isotopic compositions of kimberlite carbonates, however, are enriched in O¹⁸ by several permil with respect to those of carbonates from the subvolcanic type of carbonatite.The data suggest that not all carbonatite, kimberlite and diamond occurrences have the same average carbon isotopic composition and that significant differences exist between them. Carbon isotopic composition measurements available for the East African Rift system suggest geographic and/or tectonic groupings e.g. carbonate lavas, tuffs and intusive carbonatites associated with the Eastern Rift yield a range of δC¹³ values from ?5.8 to ?7.4%., similar to that of the carbonate rocks associated with the Western Rift volcanism (?5.8 to ?7.9%.). In contrast the interrift area encompassing Lakes Victoria, Malawi (Nyasa) and Chilwa, apparently are characterized by carbonatitic carbonates of higher C¹³ content (?2.4 to ?4.4%.).If carbonatite and kimberlite carbonates as well as diamonds represent deep seated carbon, the mean isotopic composition of this carbon is estimated as ?5.2%. and the range is ?2 to ?8%. The selection of any particular value within this range to be used as a criterion of deep-seated origin is at the moment not warranted. Indeed, the choice of any specific composition for such carbon may be meaningless, as the source of kimberlite, carbonatite and diamond carbon may not be isotopically uniform.     

The effect of net-transfer reactions on the isotopic composition of minerals

To interpret correctly the isotopic composition of metmorphic rocks and minerals, the effect of nettransfer reactions must be quantitatively evaluated. Such evaluation requires a complete set of linearly independent, net-transfer reactions that fully describe the reacting system. The set of net-transfer reactions is then coupled with mass-balance equations for stable isotopes. Reaction spaces can be contoured with isopleths of °¹⁸O, °¹³C, and D of minerals which allows evaluation of the effect of different reactions and bulk compositions on the stable isotopic composition of minerals and rocks. Using this approach, we examined the effect of fractionation of isotopes due to net-transfer reactions at the biotite and second-sillimanite isograds in northern New England. Our analysis shows that the shift in °¹³C and °¹⁸O at an isograd depends strongly upon the overall net-transfer reaction at the isograd and the bulk composition of the rock. The use of model isograd reactions to determine isotopic shifts, therefore, can lead to serious errors in the interpretation of isotopic data. At the second-sillimanite isograd °¹⁸O _qtz (quartz), °¹⁸O _kspar (K feldsdpar), and °¹⁸O _wr (whole rock) decrease by 0.5, 1.0, and 0.8 per mil, respectively. Quantitative evaluation of the effect of fractionation of isotopes by net-transfer reactions shows that: (1) the relative changes in oxygen isotopes across the isograd could be caused by distillation of fluids during develatilization reactions; (2) the magnitude of the observed isotopic shifts often differs by a factor of 2 from the calculated shifts due to reaction progress alone. The difference between observed and calculated shifts is attributed to either, differences in bulk composition between individual rocks, or, to isotopic exchange between minerals after peak metamorphism. At the biotite isograd the shifts in carbon and oxygen isotope values are different from predicted shifts caused by net-transfer reactions alone. This discrepancy suggests that fluids infiltrated the rocks during the formation of the biotite isograd.     

Early diagenetic processes during Mn-carbonate formation: evidence from the isotopic composition of authigenic Ca-rhodochrosites of the Baltic Sea

The formation of authigenic Ca-rich rhodochrosite (ACR) in sapropelic sediments of the Gotland Basin, Baltic Sea, is governed by deepwater renewal processes whereby saline water from the North Atlantic flushes the brackish anoxic Baltic Deeps. The carbon and oxygen isotopic compositions of these Mn-carbonates suggest that ACR formation takes place just below the sediment surface and that dissolved compounds from the deepwater column, such as water and bicarbonate molecules, were incorporated in ACR during authigenesis. Porewaters near the sediment surface display δ¹⁸O values of −5.4‰ (VSMOW) and are generally depleted in ¹⁸O, compared to the oxygen isotopic composition of water in equilibrium with Mn-carbonate solid solutions (ACR δ¹⁸O values are −4.6‰). This suggests that early burial diagenetic processes significantly modify the initial isotopic composition of water during Mn-carbonate formation. The reduction of sulfate having δ¹⁸O values of +8.4‰ accounts for a permanent enrichment of porewater ¹⁸O and observed δ¹⁸O values at depth equal to −4.6‰. However, this process does not explain the observed disequilibrium in the oxygen isotopic composition between water and ACR close to the sediment surface where Mn-carbonate formation takes place. Based on isotopic mass balance calculations, we suggest that MnO₂ with δ¹⁸O values of +8.9‰ released oxygen enriched in ¹⁸O into the anoxic porewaters close below the sediment surface. This process should occur after oxygenation events during deepwater renewal when MnO₂ accumulates at the surface of anoxic sediments. Manganese carbonates formed in these waters display δ¹⁸O values of ∼1.0‰ heavier than values expected solely from the initial deepwater composition. This quantitatively explains the discrepancy between paleosalinities calculated from ACR δ¹⁸O based on Mn-carbonate/water isotopic equilibrium fractionation and direct observations for the same period. Our results emphasize the important role of microbial MnO₂ reduction during rhodochrosite authigenesis and suggest that Mn(II) activity, rather than alkalinity, is the limiting component for sedimentary Mn-carbonate formation.     

Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.     

Geochemical and isotopic characteristics of fluids in the Niutuozhen geothermal field,North China

Niutuozhen geothermal field is located in the Jizhong graben, belonging to the northern part of Bohai Bay Basin in North China. Chemical and isotopic analyses were carried out on 14 samples of the geothermal fluids discharged from Neogene Minghuazhen (Nm), Guantao (Ng), and Jixianian Wumishan (Jxw) formations. The δ²H and δ¹⁸O in water, δ¹³C in CH₄, δ¹³C in CO₂, and ³He/⁴He ratio in the gases were analyzed in combination with chemical analyses on the fluids in the Niutuozhen geothermal field. The chemical and isotopic compositions indicate a meteoric origin of the thermal waters. The reservoir temperatures estimated by chemical geothermometry are in the range between 60 and 108 °C. The results show that the gases are made up mainly by N₂ (18.20–97.42 vol%), CH₄ (0.02–60.95 vol%), and CO₂ (0.17–25.14 vol%), with relatively high He composition (up to 0.52 vol%). The chemical and isotopic compositions of the gas samples suggest the meteoric origin of N₂, predominant crustal origins of CH₄, CO₂, and He. The mantle-derived He contributions are calculated to be from 5 to 8% based on a crust–mantle binary mixing model. The deep temperatures in the Jxw reservoir were evaluated based on gas isotope geothermometry to be in the range from 141 to 165 °C. The mantle-derived heat fraction in the surface heat flow is estimated to be in the range of 48–51% based on ³He/⁴He ratios.     

Carbon and oxygen isotopic composition of the Vendian-Cambrian carbonate rocks and paleoecological reconstructions

The carbon isotopic composition of carbonate rocks is widely used for the reconstruction of sedimentation paleoenvironment. Of special interest is the study of the Upper Proterozoic-Cambrian interval—the turning point in the Earth’s geological evolution. Rocks of this age show the widest variations in the carbon isotopic composition of carbonates typically correlated with epochs of global glaciations and change in the CO₂ regime. In this paper, we attempted to show that carbon isotopic variations often indicate postsedimentary alterations of carbonates and reflect the specific geochemical transformations of the rocks. Study of variations of carbon and oxygen isotopic compositions in the Vendian-Cambrian rocks provide insight into lithogenetic processes.     

Oxygen isotopic signature of 4.4-3.9 Ga zircons as a monitor of differentiation processes on the Moon

We report oxygen isotopic compositions for 14 zircon grains from a sample of sawdust from lunar breccia 14321. The zircons range in age from ∼4.4 to 3.9 Ga and in U and Th content from a few to several hundred ppm. As such these grains represent a range of possible source rocks, from granophyric to mafic composition, and cover the total age range of the major initial lunar bombardment. Nevertheless, results show that the oxygen isotopic compositions of the zircons fall within a narrow range of δ¹⁸O of about 1 per mil and have δ¹⁸O values indistinguishable from those observed for terrestrial mid-ocean ridge basalts confirming the coincidence of lunar and Earth oxygen isotopic compositions. In the δ¹⁷O vs. δ¹⁸O, coordinates data form a tight group with a limited trend on the terrestrial fractionation line. The zircon oxygen isotopes show minimal evidence of the extreme and variable mineral differentiation and element fractionation that have contributed to the formation of their parent rocks.     

Lithium isotopic composition and concentration of the upper continental crust

The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ⁷Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ⁷Li and the clay content of shales (as measured by Al₂O₃/SiO₂), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ⁷Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ⁷Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ⁷Li of −5‰ to + 5‰), with an average (δ⁷Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ⁷Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al₂O₃, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.     

Magnesium isotopic composition of the Earth and chondrites

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ²⁵Mg and ±0.07‰ on δ²⁶Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL).Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ²⁵Mg = −0.13 ± 0.05 (2SD) and δ²⁶Mg = −0.26 ± 0.07 (2SD) for global oceanic basalts (n = 110) and δ²⁵Mg = −0.13 ± 0.03 (2SD) and δ²⁶Mg = −0.25 ± 0.04 (2SD) for global peridotite xenoliths (n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ²⁵Mg = −0.15 ± 0.04 (2SD) and δ²⁶Mg = −0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes.Collectively, the Mg isotopic composition of the Earth’s mantle, based on oceanic basalts and peridotites, is estimated to be −0.13 ± 0.04 for δ²⁵Mg and −0.25 ± 0.07 for δ²⁶Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.     

Hydrothermal flow systems in the Midcontinent Rift: oxygen and hydrogen isotopic studies of the North Shore Volcanic Group and related hypabyssal sills,Minnesota

Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ¹⁸O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ¹⁸O and water content, which suggests that elevated δ¹⁸O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ¹⁸O_H2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δD_H2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δD_H2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ¹⁸O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ¹⁸O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ¹⁸O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.     

Low-temperature isotopic exchange in obsidian: Implications for diffusive mechanisms

While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more poorly understood. This paper presents the results of a series of isotopic exchange experiments aimed at further elucidating this process and determining the extent to which a point-by-point analysis of the D/H or ¹⁸O/¹⁸O isotopic composition across the hydrated rim on a geological or archaeological obsidian sample can be used as a paleoclimatic monitor. Experiments were performed by first hydrating the glass for 5 days in water of one isotopic composition, followed by 5 days in water of a second composition. Because waters of near end-member compositions were used (nearly pure ¹H₂¹⁶O, ¹H₂¹⁸O, and D₂¹⁶O), the relative migration of each species could be ascertained easily by depth-profiling using secondary ion mass spectrometry (SIMS). Results suggest that, during hydration, both the isotopic composition of the waters of hydration, as well as that of intrinsic water remaining from the initial formation of the glass vary dramatically, and a point-by-point analysis leading to paleoclimatic reconstruction is not feasible.     

Carbonates in CM2 chondrites: constraints on alteration conditions from oxygen isotopic compositions and petrographic observations

High-precision measurements of the oxygen isotopic compositions of carbonates (calcite and dolomite) from five CM2 chondrites are presented and put into context of the previously determined mineralogic alteration index (MAI), which places these meteorites into an alteration sequence. The carbonate oxygen isotopic compositions range from +20.0 to +35.7‰ for δ¹⁸O, +8.0 to +17.7‰ for δ¹⁷O, and −0.7 to −2.7‰ for Δ¹⁷O. Carbonate Δ¹⁷O values are inversely correlated with MAI and track the evolution of fluid composition from higher to lower Δ¹⁷O values with increasing alteration on the CM parent body. Similar Δ¹⁷O values for calcite and dolomite fractions from the same splits of the same meteorites indicate that calcite and dolomite in each split precipitated from a single fluid reservoir. However, reversed calcite dolomite fractionations (δ¹⁸O_dol − δ¹⁸O_cc) indicate that the fluid was subject to processes, such as freeze-thaw or evaporation, that fractionated isotopes in a mass-dependent way. Consideration of the carbonate isotopic data in the context of previously proposed models for aqueous alteration of carbonaceous chondrites has provided important insights into both the evolving alteration conditions and the utility of the models themselves. The data as a whole indicate that the isotopic evolution of the fluid was similar to that predicted by the closed-system, two-reservoir models, but that a slightly larger matrix-water fractionation factor may apply. In the context of this model, more altered samples largely reflect greater reaction progress and thus probably indicate more extended times of fluid exposure. Petrographic observations of carbonates reveal a trend of variable carbonate morphology correlated with alteration that is also consistent with changes in the duration of fluid-rock interaction. The data can also be reconciled with fluid-flow models in a restricted region of the parent body, which is consistent with assertions that the different types of carbonaceous chondrites derive from different regions of their parent bodies. In this case, the model results for a 9-km-radius body, and our data place the location of the CM chondrite formation in a 100-m-thick zone 1 km from the surface. The size of this zone could be increased if the model parameters were adjusted.     

Constraints on the petrogenesis of Martian meteorites from the Rb-Sr and Sm-Nd isotopic systematics of the lherzolitic shergottites ALH77005 and LEW88516

Detailed Rb-Sr and Sm-Nd isotopic analyses have been completed on the lherzolitic shergottites ALH77005 and LEW88516. ALH77005 yields a Rb-Sr age of 185 ± 11 Ma and a Sm-Nd age of 173 ± 6 Ma, whereas the Rb-Sr and Sm-Nd ages of LEW88516 are 183 ± 10 and 166 ± 16 Ma, respectively. The initial Sr isotopic composition of ALH77005 is 0.71026 ± 4, and the initial ε_Nd value is +11.1 ± 0.2. These values are distinct from those of LEW88516, which has an initial Sr isotopic composition of 0.71052 ± 4 and an initial ε_Nd value of +8.2 ± 0.6. Several of the mineral and whole rock leachates lie off the Rb-Sr and Sm-Nd isochrons, indicating that the isotopic systematics of the meteorites have been disturbed. The Sm-Nd isotopic compositions of the leachates appear to be mixtures of primary igneous phosphates and an alteration component with a low ¹⁴³Nd/¹⁴⁴Nd ratio that was probably added to the meteorites on Mars. Tie lines between leachate-residue pairs from LEW88516 mineral fractions and whole rocks have nearly identical slopes that correspond to Rb-Sr ages of 90 ± 1 Ma. This age may record a major shock event that fractionated Rb/Sr from lattice sites located on mineral grain boundaries. On the other hand, the leachates could contain secondary alteration products, and the parallel slopes of the tie lines could be coincidental.Nearly identical mineral modes, compositions, and ages suggest that these meteorites are very closely related. Nevertheless, their initial Sr and Nd isotopic compositions differ outside analytical uncertainty, requiring derivation from unique sources. Assimilation-fractional-crystallization models indicate that these two lherzolitic meteorites can only be related to a common parental magma, if the assimilant has a Sr/Nd ratio near 1 and a radiogenic Sr isotopic composition. Further constraints placed on the evolved component by the geochemical and isotopic systematics of the shergottite meteorite suite suggest that it (a) formed at ∼4.5 Ga, (b) has a high La/Yb ratio, (c) is an oxidant, and (d) is basaltic in composition or is strongly enriched in incompatible elements. The composition and isotopic systematics of the evolved component are unlike any evolved lunar or terrestrial igneous rocks. Its unusual geochemical and isotopic characteristics could reflect hydrous alteration of an evolved Martian crustal component or hydrous metasomatism within the Martian mantle.     

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.     

The osmium isotopic composition of convecting upper mantle deduced from ophiolite chromites

Chromites separated from the upper mantle or lower crustal portions of 18 ophiolites ranging in age from 900 Ma to 50 Ma are examined for Re-Os isotopic systematics. The ophiolites include both MORB and back arc types, although most are from supra-subduction zone (SSZ) settings. The chromites are robust indicators of the initial Os isotopic compositions of the systems sampled. There is very limited range in calculated initial γ_Os values, with the entire group averaging +1.31. Least squares linear regression of the age of chromite formation (in Ga) versus initial ¹⁸⁷Os/¹⁸⁸Os of a filtered suite yields a slope of −0.0058±0.0019 (2σ) and a present day intercept of 0.12809±0.00085 (2σ), equivalent to a γ_Os value of +0.9±0.6. Of the suite of 51 samples analyzed, 68% lie within ±1% of this evolution trajectory.Although most of the samples formed in SSZ environments, there is little evidence to suggest modification of the mantle Os isotopic composition via radiogenic melts or fluids derived from subducting slabs. The ophiolite data are interpreted as representative of the convecting upper mantle and suggest that the present isotopic composition of the convecting upper mantle averages approximately 1.2% less radiogenic than the estimated minimum composition of the primitive upper mantle of 0.1296±8 (Meisel et al., 2001). The most likely explanation for the difference is the formation, subduction and isolation of some portion of the mafic oceanic crust. Using models based on the assumption that the convecting upper mantle comprises 50% of the total mass of the mantle, and that the average isolation period for subducted oceanic crust is 1.5 to 2.0 Ga, it is estimated that approximately 2 to 3% of the total mass of the mantle is composed of subducted mafic oceanic crust that remains isolated from the convecting upper mantle. Because the isotopic compositions of the DMM and PUM overlap within uncertainties, however, the results do not require any isolated slab component.