Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

Eclogite-facies fluid infiltration: constraints from δ18O zoning in garnet

In situ analysis reveals that eclogite-facies garnets are zoned in δ¹⁸O with lower values in the core and rims that are ~1.5 to 2.5 ‰ higher. This pattern is present in 9 out of 12 garnets analyzed by SIMS from four orogenic eclogite terranes, and correlates with an increase in the mole fraction of pyrope and Mg/Fe ratio from core to rim, indicating prograde garnet growth. At the maximum temperatures and the time-scales experienced by these garnets, calculated intragranular diffusion distances for oxygen are small (<5 μm), indicating that δ¹⁸O records primary growth zoning and not diffusive exchange. The oxygen isotope gradients are larger than could form due to temperature changes during closed-system mineral growth. Thus, gradients reflect the compositions of fluids infiltrating during prograde metamorphism. Values of δ¹⁸O in garnet cores range from ?1 to 15 ‰, likely preserving the composition of the eclogite protoliths. Two garnet cores from the Almenningen eclogite in the Western Gneiss Region, Norway, have δ¹⁸O ~?1 ‰ and are the first negative δ¹⁸O eclogites identified in the region. In contrast with orogenic eclogites, seven high δ¹⁸O garnets (>5 ‰) from two kimberlites are homogeneous in δ¹⁸O, possibly due to diffusive exchange, which is possible for prolonged periods at higher mantle temperatures. Homogeneity of δ¹⁸O in garnets outside the normal mantle range (5–6 ‰) may be common in kimberlitic samples.     

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

Fluid Composition, δD of Channel H2O,and δ18O of Lattice Oxygen in Beryls: Genetic Implications for Brazilian,Colombian, and Afghanistani Emerald Deposits

The fluid composition, δD of channel H₂O, and δ₁₈O of lattice oxygen have been determined in beryl and emerald from a variety of geological environments and used to constrain the origin of the parental fluids from which beryl has grown. Step-heating analyses performed by quadrupolar mass spectrometry were used to quantify the composition of the fluid phases in beryl from granitic pegmatites and greisens and emerald from Brazil, Colombia, and Afghanistan. An important conclusion is that beryl and emerald have a similar fluid composition, with concentrations of H₂O being greater than 90% of the total water in the mineral irrespective of the age of formation (2.0 Ga to 32 Ma) and tectonic settings. However, the Brazilian Santa Terezinha shear-zone emerald deposit contains abundant CO₂, up to 13 wt% of the total fluid. A second conclusion is that the channel H₂O content for some Brazilian emeralds is higher than the range defined for beryl in the literature, especially for those related to the shear-zone type (2.99 lt; H₂O < 3.16 wt%) and the pegmatite type from the Pombos, Pela Ema, and Pirenopolis deposits (2.78 < H₂O < 3.01 wt%). Colombian emeralds have very low H₂O contents (1.30 < H₂O < 1.96 wt%), among the lowest in the world.

Brazilian, Colombian, and Afghanistani emeralds have contrasting and restricted ranges of δ¹⁸O values. In Brazil, emeralds related to pegmatites have a systematic δ¹⁸O inter-deposit variability (+6.3 < δ¹⁸O < +12.4‰). The calculated δ¹⁸O of the fluid was buffered by the host ultrabasic rocks during fluid-rock interaction. Emerald and cogenetic phlogopite related to shear-zone-type deposits have a quite restricted δ¹⁸O range (+12.0 < δ¹⁸O 7lt; +12.4‰); the calculated is interpreted to represent the original isotopic composition of the hydrothermal fluid. Relative to Brazil, the δ¹⁸O of Colombian and Afghanistani emeralds shows strong enrichment in ¹⁸O (+13.4 < δ¹⁸O < +23.6‰), and the high calculated δ¹⁸O of the fluid suggests extensive reaction with 18O-rich sedimentary or metasedimentary rocks.

In Brazil, the δD composition of channels in emerald and the calculated δ¹⁸O^H₂O for phlogopite are compatible with both magmatic and metamorphic origins. A magmatic origin is supported for emeralds associated with the pegmatitic Socotó and Carnaiba deposits (mean δD = ?37.8 ± 8‰) and a metamorphic origin is suggested for the Santa Terezinha shear-zone type (mean δD = ?32.4 ± 3‰). A metamorphic origin is proposed for Colombian emeralds. Afghanistani emeralds have a δD composition of channels (mean δD = ?46.3 ± 1.3‰) that is compatible with both magmatic and metamorphic origins.     

Continental-scale patterns in modern wood cellulose δO: Implications for interpreting paleo-wood cellulose δO

The isotopic composition of ancient wood may be a useful archive of some climatic or geochemical conditions of the past, but presently there are many uncertainties that constrain such interpretations. We sampled naturally growing, predominantly native trees in forested regions of North America and the Caribbean to evaluate the strength of the relationships among cellulose δ¹⁸O (δ¹⁸O_cel), relative humidity (RH), precipitation δ¹⁸O (δ¹⁸O_ppt), and mean annual temperature (MAT) at the continental scale, and the general range of variability in δ¹⁸O_cel associated with site hydrologic conditions and species differences. We found up to 4‰ differences among different species growing at the same site, that conifer cellulose at a site is more enriched than angiosperm cellulose by 1.5‰ (p < 0.001), and that differences in landscape position, reflecting differing access to the water table, produced differences of <1‰ in δ¹⁸O_cel. At the continental scale, δ¹⁸O_cel was strongly influenced by modeled δ¹⁸O_ppt (R² = 0.80, p < 0.001). Average summer minimum RH (RH_min) combined with δ¹⁸O_ppt explained more of the variability (R² = 0.93, p < 0.001) in δ¹⁸O_cel across North American and Caribbean forests. MAT and δ¹⁸O_cel were also strongly correlated across North America (R = 0.91 and 0.95, p < 0.001, for angiosperms and conifers, respectively). The difference between δ¹⁸O_ppt and δ¹⁸O_cel is not constant (varying from 35-44‰) and is inversely correlated with δ¹⁸O_ppt. The relationships among δ¹⁸O_ppt, RH_min, δ¹⁸O_cel, and MAT established for North America and the Caribbean applied reasonably well when δ¹⁸O_cel was used to estimate MAT and δ¹⁸O_ppt in Asia, Europe, and South America, but there were important exceptions. The most accurate predictions of MAT and δ¹⁸O_ppt from δ¹⁸O_cel require RH_min. Predictions of δ¹⁸O_ppt and MAT made from δ¹⁸O_cel alone produced errors of up to 8‰ and 16 °C, respectively.     

Variations in δ18O, δD,and the concentration of pollen and spores in an autochthonic heterogeneous massive ice on the Erkutayaha River in the southern part of the Yamal Peninsula

Doklady Earth Sciences -     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Variations in composition and δ18O values within the Kaffo albite—Riebeckite granite of Liruei Complex,Younger Granites of Nigeria

The peralkaline Kaffo albite—riebeckite granite is an albitised, low-temperature intrusion in Liruei Complex, one of the oldest of the ring-complexes in the Younger Granite province of Nigeria. Analyses of borehole samples from different parts of the intrusion show it to be compositionally heterogeneous, especially in respect of Si, Al, Na, K and F distribution and this, in part, can be correlated with the variable degree of albitisation. Isotopically the granite is a normal plutonic type with δ¹⁸ O values of $\text{+ 8.1 ± 0.2‰}$, and albitisation does not seem to have been accompanied by exchange of isotopes between albitising fluid and the granite. Co-existing riebeckitic-arfvedsonite and aegirine pairs from borehole samples show extreme enrichment in Na and Fe; the amphibole also shows considerable substitution of Fe by Ti, Zn and Mn, and of OH by F. Isotopically the amphibole and pyroxene are different from others, having low, variable δ¹⁸ O values (+5.3–+6.4 and $\text{+4.4–+5.1‰}$, respectively), and the fractionation value Δ Px — Am is always large, negative and constant (—$\text{1.2 ± 0.2‰}$). The low δ¹⁸ O values are considered to be due to special features of the crystal chemistry of the alkali amphiboles and pyroxenes, and the spread of each set of values may be due to sub-solidus isotope exchange between the minerals and albitising fluid.     

Late Holocene inter-annual temperature variability reconstructed from the δ18O of archaeological Ostrea angasi shells

Two multi-year oxygen isotope (δ¹⁸O) records were obtained from archaeological Ostrea angasi shells, confirming the potential of this species to provide valuable environmental records for the late Holocene period in southeastern Australia. High-resolution δ¹⁸O_shell samples from the O. angasi clearly display a seasonal variability, offering insight into past climate conditions in a region where such information is presently limited.

The oxygen isotope record in O. angasi reflects a combined temperature–salinity signal. Observations of δ¹⁸O_shell data from modern specimens are used as a point of reference to assist in decoupling these two influences, with the two archaeological samples compared with the δ¹⁸O_shell profile of four modern O. angasi. Assuming similar paleo- δ¹⁸O_water values at the collection sites, data from these archaeological shells present a record of temperatures during the period of their growth that are consistently lower than modern day, with mean annual temperatures ～2°C cooler.     

Variation of summer precipitation δ18O on the Chinese Loess Plateau since the last interglacial

Orbital-scale East Asian Summer Monsoon (EASM) variations inferred from loess deposits in northern China and speleothems from southern China display different dominant periods, complicating our understanding of monsoon response to insolation and ice-volume forcings. Here we integrate a new microcodium δ¹⁸O record from a high-resolution last interglacial loess profile with previously published data and provide a composite microcodium δ¹⁸O record on the Chinese Loess Plateau (CLP) since the last interglacial. The composite microcodium δ¹⁸O record displays distinct precessional cycles, consistent with speleothem δ¹⁸O records, but with different amplitude contrast (particularly during the peak interglacials). We propose that both loess and speleothem δ¹⁸O records exhibit covariations at precessional timescale oscillations. The discrepancy between loess and speleothem from southern China can be attributed to the influences of other processes besides summer precipitation on the proxies. A slight difference in amplitude between microcodium and speleothem δ¹⁸O records implies that the EASM is also influenced by inland surface boundary conditions, which has important impacts on the occurrence of EASM precipitation. Therefore, microcodium δ¹⁸O from the Chinese loess–paleosol sequences can be regarded as a representative proxy of EASM precipitation in northern China and then a reliable proxy reflecting the variation of EASM intensity.     

Holocene climate variability in Europe: Evidence from δ18O,textural and extension-rate variations in three speleothems

Time-series O isotope profiles for three U–Th dated stalagmites have revealed that for much of the Holocene, a site on the Atlantic seaboard (SW Ireland) exhibits first-order δ¹⁸O trends that are almost exactly out of phase with coupled δ¹⁸O curves from two southern European sites (SE France and NW Italy). In the Irish stalagmite (CC3 from Crag Cave, SW Ireland), low δ¹⁸O at 10,000 cal yr BP reflects cool conditions. By the early to mid-Holocene (9000–6000 cal yr BP) δ¹⁸O had increased, reflecting the onset of warmer conditions on the Atlantic seaboard. This shift to higher δ¹⁸O was accompanied by a marked increase in the stalagmite extension rate, reinforcing our interpretation that this was a period of relative warmth. Except for an episode of increased extension rate about 5500 yr ago, δ¹⁸O in the Crag stalagmite exhibits a gradual decrease, accompanied by declining extension rates between 7800 and 3500 cal yr BP, interpreted as a cooling trend. There is evidence for increases in both δ¹⁸O and stalagmite extension rate in the period from 3500 cal yr BP to the present day suggesting a return to warmer conditions on the Atlantic seaboard. In the stalagmite from NW Italy (ER76, Grotta di Ernesto, Trentino province) the early-Holocene (c. 9200-7800 cal yr BP) is characterised by high δ¹⁸O, probably indicative of warm and/or dry conditions. Exceptionally low δ¹⁸O from 7800 to 6900 cal yr BP at this site reflects a well-defined wet phase (Cerin wet phase). In the last three millennia, this stalagmite exhibits a shift to lower δ¹⁸O, interpreted as some combination of cooler and/or wetter conditions. Unlike the Irish stalagmite, the Italian sample does not show a correlation between δ¹⁸O and extension rate. Instead, its extension rate correlates roughly with δ¹³C, presumably reflecting a climate-driven vegetation change. In the early Holocene, δ¹⁸O in the French stalagmite (CL26, Grotte de Clamouse, Herault province, SE France) was low relative to its Holocene average. For much of the period since c. 3500 cal yr BP this stalagmite exhibits higher δ¹⁸O than in the early Holocene, suggesting warmer conditions. Like the Irish stalagmite, the French sample exhibits a well-defined correlation between δ¹⁸O and extension rate. Had drip-water availability been the dominant control on δ¹⁸O at this semi-arid site then higher δ¹⁸O would have been accompanied by lower, not higher extension rates. This suggests strongly that temperature rather than rainfall amount was the dominant control at this site. While conclusions regarding the patterns of climate variability on a continent scale must remain tentative because of the limited number of stalagmites studied we argue that early Holocene warm conditions on the Atlantic seaboard (Irish site) coincided with relatively cool conditions at the Clamouse site. By c. 3500 yr ago the pattern appears to have been reversed.     

Isotopic Composition (δ13C, δ18O) of Carbonate Concretions from Terrigenous Deposits in the Northern Caucasus

The isotopic composition of carbon and oxygen was studied in carbonate concentrations with different compositions (calcite, dolomite, and siderite) from Jurassic, Cretaceous, and Tertiary terrigenous deposits of the Northern Caucasus. Wide variations in the isotopic composition (from 41.4 to 18.1 for ¹³C and from 11.7 to 33.5 for ¹⁸O) point to different formation conditions in the early diagenesis zone and the later catagenesis zone.     

Modelling of the oxygen isotope evolution of seawater: implications for the climate interpretation of the δ18O of marine sediments

It is often argued that the δ¹⁸O value of oceanic water was maintained close to 0‰ for hundreds of millions of years, as a consequence of oxygen isotope exchange between oceanic crust and seawater. However, for several decades, the interpretation of the biosedimentary oxygen isotope record has conflicted with the igneous record because, with increasing age, a general trend of decreasing δ¹⁸O values (about 6‰) is observed in most carbonates, cherts and phosphates, especially for the Paleozoic and early Mesozoic. We developed a dynamical model of seawater-crust interaction that computes the δ¹⁸O value in these two reservoirs as function of time. This model takes into account the continuous production of crust at oceanic ridges, its expansion rate, the permeability profile with space and time, the mineralogical mode of the crust, and the kinetics of oxygen isotope exchange between rock-forming minerals and seawater. The model indicates that the δ¹⁸O value of seawater may vary by ±2‰ with a time response ranging from 5 to 50 Ma for expansion rates of 1 to 10 cm.a⁻¹. The variation of ±2‰ is fixed by both integrated water-rock ratio and closure time of the seawater-crust system by sediments. Variations in the oxygen isotope ratio of seawater through time have important implications for the interpretation of the systematically low δ¹⁸O values of pre-Jurassic marine sediments. According to our model, marine paleotemperatures could be up to 10°C lower than those expected when applying the classical hypothesis of an ice-free ocean with a δ¹⁸O value of −1‰.     

The δ18O and δ13C records in an aragonite stalagmite from Furong Cave,Chongqing, China: A-2000-year record of monsoonal climate

A 7-cm long aragonite stalagmite, FR0510-1, from Furong Cave, Chongqing, was dated by ²¹⁰Pb and ²³⁰Th methods, revealing a-2000-year record of climate history under the influence of the East Asian Monsoon. The FR0510-1 record resembles Dongge Cave DA record on 10–100-year scales, but quite different from the Wanxiang Cave WX42B record, indicating that while stalagmite δ¹⁸O record represents local/regional moisture change, spatial variability of the monsoonal rainfall over eastern China must take into account. During the past 2000 years, climate in Chongqing was relatively wet in the intervals of 50 BC–AD 250, AD 1150–1450 and AD 1600–1950, and relatively dry during the periods of AD 250–1150 and AD 1450–1600. Dry conditions were prevailing over the Medieval Warm Period, whereas wet climates were dominant during the most time of the Little Ice Age in Chongqing area.