Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Stable isotope of some selected Egyptian pectinids and their paleoenvironmental implications

Eight pectinid shells were collected and subjected to quantitative study using δ¹⁸O and δ¹³C isotopic analysis in order to study the paleoenvironment which prevailed during their calcification. The scalerochronological variations in δ¹⁸O and δ¹³C values, among these shells are also discussed. The Early Miocene pectinid shells display highly depleted δ¹⁸O and δ¹³C signature as a result of paleo-meteoric water with heavy rainfall that was produced by Tropical Cyclones when the Mediterranean Sea was open. The Early Pliocene pectinid shells reveal depleted δ¹⁸O values, related to the influx of fresh water influenced by monsoonal activity following the formation of the Tibetan Plateau. Their enrichment in the δ¹³C isotopic excursion is referred to high productivity of the Indian Ocean, which was the main source of the Red Sea water. The Pleistocene pectinid shell shows highly depleted δ¹⁸O and δ¹³C signature with obvious diagenetic shell structure, indicating that a wetter humid climate prevailed during the Early–Middle Pleistocene and long sub-arial exposure of the shell. The Recent Mediterranean pectinid shell displays slight enrichment in δ¹⁸O and δ¹³C values referring to deeper inhabitation of this species with a low temperature and high salinity environment. The scalerochronological variations in both δ¹⁸O and δ¹³C values, along these shells is referred to seasonal variations or kinetic effects.     

Controls, variation, and a record of climate change in detailed stable isotope record in a single bryozoan skeleton

The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ¹⁸O) in 61 subsamples (along three branches of a single unaltered colony) range from −0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ¹³C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ¹⁸O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ¹⁸O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ¹⁸O and 1.34 in δ¹³C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

Early‐middle Holocene land snail shell stable isotope record from Grotta di Latronico 3 (southern Italy)

This paper compares stable isotope (δ¹⁸O and δ¹³C) records of early–middle Holocene land snail shells from the archaeological deposits of Grotta di Latronico 3 (LTR3; southern Italy) with modern shell isotopic data. No substantial interspecific variability was observed in shell δ¹⁸O (δ¹⁸Os) of modern specimens (Pomatias elegans, Cornu aspersum, Eobania vermiculata, Helix ligata and Marmorana fuscolabiata). In contrast, interspecific shell δ¹³C (δ¹³Cs) variability was significant, probably due to different feeding behaviour among species. The δ¹⁸Os values of living land snails suggest that species hibernate for a long period during colder months, so that the signal of ¹⁸O‐depleted winter rainfall in their δ¹⁸Os is lost. This suggests that δ¹⁸Os and δ¹³Cs values of Pomatias elegans from this archaeological succession provide valuable clues for seasonal (spring–autumn) climatic conditions during the early–middle Holocene. The δ¹⁸Os values of fossil specimens are significantly lower than in modern shells and in agreement with other palaeoclimatic records, suggesting a substantial increase of precipitation and/or persistent changes in air mass source trajectories over this region between ca. 8.8 cal ka BP and 6.2–6.7 ka ago. The δ¹³Cs trend suggests a transition from a slightly ¹³C‐enriched to a ¹³C‐depleted diet between early and middle Holocene compared to present conditions. We postulate that this δ¹³Cs trend might reflect changes in the C3 vegetation community, potentially combined with other environmental factors such as regional moisture increase and the progressive decrease of atmospheric CO₂ concentration. Copyright © 2010 John Wiley & Sons, Ltd.     

Paleoclimatic implications of the spatial patterns of modern and LGM European land-snail shell δO

The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ¹⁸O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ¹⁸O between sites but not among genera at a single location. Therefore, we group δ¹⁸O values from different genera together to map the spatial distribution of δ¹⁸O in shell carbonate. Shell δ¹⁸O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ¹⁸O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ¹⁸O data show a different gradient with δ¹⁸O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ¹⁸O values decreasing northward.     

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.     

Stable isotope variations in modern tropical speleothems: Evaluating equilibrium vs. kinetic isotope effects

Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ¹⁸O and δ¹³C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ¹³C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The ¹³C depletions are likely caused by kinetically driven departures in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions, caused by rapid calcite growth. ¹³C enrichments can be accounted for by Rayleigh distillation of the HCO₃⁻ (aq) reservoir during degassing of ¹³C-depleted CO₂.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in ¹⁸O relative to equilibrium values. δ¹⁸O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ¹³C, δ¹⁸O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO₂ hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO₃⁻ (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in ¹⁸O enrichment in the HCO₃⁻ (aq) reservoir and ultimately in the precipitated CaCO₃.     

Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

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.     

Isotopic evidence for the incorporation of methane-derived carbon into foraminifera from modern methane seeps, Hydrate Ridge, Northeast Pacific

The presence of modern methane seeps at Hydrate Ridge, offshore Oregon, provide an opportunity to study the influence of methane seeps on the ecology and geochemistry of living foraminifera. A series of cores were collected from the southern summit of Hydrate Ridge in 2002. Samples were preserved and stained to determine the δ¹³C composition of three species of live (stained) and dead benthic foraminifera: Uvigerina peregrina, Cibicidoides mckannai, and Globobulimina auriculata. Specimens were examined under light and Scanning Electron Microscopy (SEM) and exhibit no evidence of diagenesis or authigenic carbonate precipitation. Individual living foraminifera from seep sites recorded δ¹³C values from −0.4‰ to −21.2‰, indicating the isotopic influence of high methane concentrations. Average δ¹³C values (calculated from single specimens) range from −1.28 to −5.64‰ at seep sites, and −0.81 to −0.85‰ at a control (off seep) site.Two distinct seep environments, distinguished by the presence of microbial mats or clam fields, were studied to determine environmental influences on δ¹³C values. Individual foraminifera from microbial mat sites exhibited more depleted δ¹³C values than those from clam field sites. We interpret these differences as an effect of food source and/or symbiotic microbes on foraminiferal carbon isotopic values, acting to magnify the negative δ¹³C values recorded via the DIC pool. No statistical difference was found between δ¹³C values of live vs. dead specimens. This suggests that authigenic carbonate precipitation did not play a dominant role in the observed isotopic compositions. However, a few dead specimens with extremely negative δ¹³C composition (<-12‰) do indicate potential evidence for an authigenic influence on the recorded δ¹³C composition.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

Sea-rain-lake relation in the Last Glacial East Mediterranean revealed by δO-δC in Lake Lisan aragonites

We investigated the Sea-Rain-Lake relation during the Last Glacial-Holocene in the East Mediterranean region by comparing the δ¹⁸O and δ¹³C records of authigenic aragonite deposited in Lake Lisan, the Dead Sea, Mediterranean foraminifera, and speleothems. The Lisan Formation data display long- and short-term variations of δ¹⁸O, representing steady-state conditions of the lake (e.g., 5.6‰ ± 0.5‰ and 4.5‰ ± 1‰ in the Upper and Lower Members of the Lisan Formation, respectively), and short-term excursions reflecting large floods and droughts. The long-term (steady-state) δ¹⁸O values of the Lisan aragonites show similarity to the corresponding time-equivalent records of the Eastern Mediterranean foraminifera and Judea Mountain speleothems: The Last Glacial deposits are in all of them 2‰-3‰ heavier than the Holocene ones. We interpret this similarity as reflecting the significance of the source effect on the long-term behavior of isotopic reservoirs: Speleothem δ¹⁸O is strongly influenced by the marine reservoir that contributes its vapor to rain formation; the lake δ¹⁸O is dominated by the composition of the inflowing water. Short-term variations in the isotopic composition of rainfall are dominated by the amount effect and the temperature and those of the Lake’s upper water mass by the lake’s water balance.δ¹³C values are more variable than δ¹⁸O in the same Lisan sequences (e.g., δ¹³C in the Lower Member is 1.0‰ ± 1.7‰, whereas δ¹⁸O is 4.6‰ ± 0.7‰) and are 1‰ to 1.5‰ higher in the Upper Member than in the Lower and Middle Members of the Lisan Formation. These variations reflect significant increase in primary productivity of the lake and algal bloom activity. It appears that the hypersaline-saline lakes were not as “dead” as the Dead Sea is and that algal activity had an important impact upon the geochemistry of Lake Lisan.The δ¹⁸O data combined with independent geochemical and limnologic information (e.g., level fluctuations) indicate that Lisan time was characterized by high precipitation-high lake stands-high atmospheric humidity, whereas the Holocene Dead Sea shows the opposite behavior. This paleoclimatic reconstruction is consistent with independent evidence for significantly wetter conditions in the East Mediterranean region during the Last Glacial period.     

Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ¹³C and δ¹⁸O values of carbonates from the Atacama are the highest of any desert in the world. δ¹³C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO₂ production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ¹³C value of soil carbonate in the Atacama, whereas the fraction C₃ to C₄ biomass at individual sites has a subordinate influence. The high average δ¹³C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO₂.δ¹⁸O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ¹³C values. δ¹⁸O values for soil carbonate predicted from local temperature and δ¹⁸O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ¹⁸O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.     

Behavior of carbonate-associated sulfate during meteoric diagenesis and implications for the sulfur isotope paleoproxy

Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ³⁴S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ¹⁸O values decrease across these same fronts. The δ¹³C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ¹³C during sea-level lowstand. Conversely, δ³⁴S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ³⁴S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.     

Environmental significance of C/C and O/O ratios of modern land-snail shells from the southern great plains of North America

¹³C/¹²C and ¹⁸O/¹⁶O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ¹⁸O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ¹³C values ranged from −13.2‰ to 0.0‰. δ¹⁸O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ¹⁸O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ¹⁸O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ¹³C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ¹³C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C₃, C₄) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.     

Diamond growth from oxidized carbon sources beneath the Northern Slave Craton, Canada: A δC-N study of eclogite-hosted diamonds from the Jericho kimberlite

Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ¹³C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ¹³C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ¹³C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ¹³C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ¹³C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ¹³C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ¹³C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ¹³C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ¹³C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ¹³C-N yielded a partition coefficient (K_N) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ¹³C values of diamond cores (−4‰) dictate the growth medium had higher δ¹³C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.     

Paleoenvironment of the Folsom archaeological site, New Mexico, USA, approximately 10,500 C yr B.P. as inferred from the stable isotope composition of fossil land snail shells

Well-preserved aragonitic land snail shells (Vallonia) from late Pleistocene Eolian sediment in the Folsom archaeological site in New Mexico exhibit an overall decrease of δ¹⁸O_PDB from maximum values of +2.7‰ (more positive than modern) to younger samples with lower average values of about −3.6‰ (within the modern range). The age of the samples (approximately 10,500 ¹⁴C yr B.P.) suggests that the decrease in δ¹⁸O may manifest climatic changes associated with the Younger Dryas. Some combination of increased relative humidity and cooler temperatures with decreased δ¹⁸O of precipitation during the times of snail activity can explain the decrease in shell δ¹⁸O. A well-known Paleoindian bison kill occurred at the Folsom site during this inferred environmental transition.Average δ¹³C values of the aragonite shells of the fossil Vallonia range from −7.3 to −6.0‰ among different archaeological levels and are not as negative as modern values. This suggests that the proportion of C₄ vegetation at the Folsom site approximately 10,500 ¹⁴C yr B.P. was greater than at present; a result which is consistent with other evidence for higher proportions of C₄ plants in the region at that time.     

Isotopic Fingerprints of Paleoclimates during the Last 30,000 Years in Deep Confined Groundwaters of Southern India

Isotopic and geochemical evidence of paleoclimates, especially for the last glaciation, has been obtained from deep confined groundwaters of southern India. The δ¹³C, δ¹⁸O, chloride, and deuterium analyses of groundwaters show distinct excursions inferred to be related to climatic variations. The arid climatic episode associated with the last glaciation (18,000 ± 2000 yr B.P.) is conspicuously identified by signatures of relatively enriched δ¹³C (−10 to −12‰ PDB) and δ¹⁸O (−5.3 to −4.8‰ SMOW) values, and high chloride concentration (80 to 160 mg/l). The transition from an arid to humid period ca. 12,000–8000 yr B.P. is shown by a decreasing trend in the δ¹³C (−9.5 to −17‰) and δ¹⁸O (−4.5 to −6.3‰) contents of groundwaters. The late Holocene (since 4000 yr B.P.), marked by a more humid but unstable climate, is identified by further depletion of δ¹³C (−13 to −20‰) and δ¹⁸O (−5.2 to −6.3‰). Similar variation between δ¹⁸O and chloride values in confined groundwaters further demonstrates two distinct climatic excursions (arid and humid) governed by the “amount effect.” This is the first time that isotopic and geochemical signatures related to changing paleoclimates have been identified in the confined groundwaters of the southern Indian landmass.     

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).