Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys

Many of the heaviest and lightest natural zinc (Zn) isotope ratios have been discovered in hydrothermal ore deposits. However, the processes responsible for fractionating Zn isotopes in hydrothermal systems are poorly understood. In order to better assess the total range of Zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation, we have measured Zn isotopes in seafloor hydrothermal fluids from numerous vents at 9–10°N and 21°N on the East Pacific Rise (EPR), the TAG hydrothermal field on the Mid-Atlantic Ridge, and in the Guaymas Basin. Fluid δ⁶⁶Zn values measured at these sites range from + 0.00‰ to + 1.04‰. Of the many physical and chemical parameters examined, only temperature was found to correlate with fluid δ⁶⁶Zn values. Lower temperature fluids (< 250 °C) had both heavier and more variable δ⁶⁶Zn values compared to higher temperature fluids from the same hydrothermal fields. We suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite (Zn sulfide), and that this process is a primary cause of Zn isotope variation in hydrothermal fluids. Thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest Zn found in fluids that were calculated to be saturated with respect to sphalerite. We have also measured Zn isotopes in chimney sulfides recovered from a high-temperature (383 °C) and a low-temperature (203 °C) vent at 9–10°N on the EPR and, in both cases, found that the δ⁶⁶Zn of chimney minerals was lighter or similar to the fluid δ⁶⁶Zn. The first measurements of Zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid δ⁶⁶Zn, and suggest that subsurface Zn sulfide precipitation is a primary factor in causing variations in fluid δ⁶⁶Zn. By understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid δ⁶⁶Zn, Zn isotopes may be used as a tracer for studying hydrothermal processes.     

Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations

The stable isotopic composition of hydrogen and oxygen (δ²H and δ¹⁸O) and tritium activity (³H) were monitored in monthly precipitation at two continental stations (Ljubljana, Zagreb) and six stations along the eastern Adriatic coasts of Slovenia and Croatia in the period 2001–2003. Mean air temperatures and amount of precipitation were also recorded.

Distinct differences in both meteorological and isotopic data between the continental and maritime stations were observed. Seasonal variations in δ¹⁸O are smaller at the maritime stations than at the continental ones due to smaller seasonal temperature variations. A good correlation between δ¹⁸O and δ²H was obtained for each station, and the local meteoric water lines are close to the Global Meteoric Water Line, with a decreasing trend of slope for the south-Adriatic stations. Good correlations between δ¹⁸O in monthly precipitation and mean monthly air temperature were observed at all stations. The slope of δ¹⁸O vs. T varied between 0.37‰ °C⁻¹ and 0.15‰ °C⁻¹. Mean ³H activity and seasonal variation of ³H activity are smaller at maritime stations than at continental ones. Additionally, ³H activity decreases in the NW–SE direction of the Adriatic coast.

The study of spatial variations over this relatively small area rich in geographical and climatic diversities showed the complexity of the isotopic composition of precipitation and the isotopic data obtained for eight stations, most of them in the karstic area along the Adriatic coast, and gave valuable information for regional hydrological investigations and modelling of isotope variability over the Mediterranean basin.     

Preliminary stratigraphic and structural architecture of Bhutan: Implications for the along strike architecture of the Himalayan system

High-precision in-situ ion microprobe (SIMS) oxygen isotope analysis of zircons from two diorite intrusions associated with the late Caledonian Lochnagar pluton in Scotland has revealed large differences in the degree of heterogeneity in zircon δ¹⁸O between the diorites. Zircon crystals from the Cul nan Gad diorite (CnG) show a unimodal distribution of oxygen isotope values (δ¹⁸O = 6.0 ± 0.6‰ (2σ)) and no or only minor grain-scale variation. Those from the Allt Darrarie diorite (AD1) show a large range in δ¹⁸O and an apparent bimodal distribution with modes of 6.6 ± 0.4‰ and 7.3 ± 0.4‰. Variations of up to 1.2‰ occur between and within grains; both an increase and decrease in δ¹⁸O with zircon growth has been observed. The δ¹⁸O composition of growing zircon can only change if open-system processes affect the magma composition, i.e. if material of contrasting δ¹⁸O composition is added to the magma. The variability in AD1 is interpreted to represent a cryptic record of magma mixing. A ‘deep crustal hot zone’ is a likely site for generation of the dioritic magmas which developed by mixing of residual melts and crustal partial melts or by melting of mafic lower crustal rocks. The overall small number of zircons with mantle-like δ¹⁸O values (5.3 ± 0.6‰ (2σ)) in the Lochnagar diorites is largely the product of crustal differentiation rather than crustal growth.

The δ¹⁸O of quartz from the CnG and AD1 diorites shows only minor variation (CnG: 10.9 ± 0.5‰ (2σ), AD1: 11.7 ± 0.6‰ (2σ)) within single populations, with no evidence of mixing. Quartz–zircon isotopic disequilibrium is consistent with later crystallisation of quartz from late magmatic fluids, and in case of the AD1 diorite after the inferred magma mixing from a homogenised, higher δ¹⁸O melt.

High-precision SIMS oxygen isotope analysis of zircon provides a new approach to identifying and resolving previously undetected early-stage magma mixing and constraining the compositions and origins of the component magmas. A combination of zircon, quartz and whole-rock data has proven to be a powerful tool in reconstructing the petrogenetic evolution of diorite from early crystallisation to late alteration.     

Stable isotope values of Costa Rican surface waters

Stable isotope data of surface waters from the humid tropics in general, and Costa Rica in particular, are scarce. To improve our understanding of the spatial distribution of stable isotopes in surface waters, we measured δ¹⁸O and δD in river and lake (n=63) and precipitation (n=3) samples from Costa Rica. We also present data from the IAEA/WMO isotopes in precipitation network as context for our study. Surface water isotope values do not strongly correlate with elevation, stream head elevation, stream length, distance from Caribbean Sea, or estimated mean annual precipitation for the country as a whole. However, the data show distinct regional trends. The δ¹⁸O and δD values downwind of mountain ranges are inversely related to the altitude of the ranges the air masses traverse. In the lee of the high Talamanca Range, δ¹⁸O values are 6–8‰ lower, while in the lee of the lower Tilarán Range δ¹⁸O values are 2–3‰ lower than upwind sites along the Caribbean Slope. An altitude effect of −1.4‰ δ¹⁸O/km is present on the Pacific slope of southern Costa Rica, equivalent to a temperature effect of −0.3‰/°C. The Nicoya and Osa Peninsulas have higher values than upwind sites, suggesting input of Pacific-sourced moisture, evaporative enrichment, or decreased condensation temperatures. Elevated and increasing d-excess values inland along the Nicaragua Trough suggest a recycled component may be an important contributor to the water budget. These data provide preliminary stable isotope information for Costa Rica, and will benefit paleoclimatic research in the region. More detailed studies would be beneficial to our understanding of the controls on stable isotope composition of tropical waters.     

Can biomass burning produce a globally significant carbon-isotope excursion in the sedimentary record?

Negative carbon-isotope excursions have been comprehensively studied in the stratigraphic record but the discussion of causal mechanisms has largely overlooked the potential role of biomass burning. The carbon-isotopic ratios (δ¹³C) of vegetation, soil organic matter and peat are significantly lower than atmospheric carbon dioxide (CO₂), and thereby provide a source of low ¹³C CO₂ when combusted. In this study, the potential role of biomass burning to generate negative carbon isotope excursions associated with greenhouse climates is modeled. Results indicate that major peat combustion sustained for 1000 yr increases atmospheric CO₂ from 2.5× present atmospheric levels (PAL) to 4.6× PAL, and yields a pronounced negative δ¹³C excursion in the atmosphere ( 2.4‰), vegetation ( 2.4‰) and the surface ocean ( 1.2‰), but not for the deep ocean ( 0.9‰). Release of CO₂ initiates a short-term warming of the atmosphere (up to 14.4 °C, with a duration of 1628 yr), which is consistent with the magnitude and length of an observed Toarcian excursion event. These results indicate that peat combustion is a plausible mechanism for driving negative δ¹³C excursions in the rock record, even during times of elevated pCO₂.     

Isotope variations in a Sierra Nevada snowpack and their relation to meltwater

Isotopic variations in melting snow are poorly understood. We made weekly measurements at the Central Sierra Snow Laboratory, California, of snow temperature, density, water equivalent and liquid water volume to examine how physical changes within the snowpack govern meltwater δ¹⁸O. Snowpack samples were extracted at 0.1 m intervals from ground level to the top of the snowpack profile between December 1991 and April 1992. Approximately 800 mm of precipitation fell during the study period with δ¹⁸O values between −21.35 and −4.25‰. Corresponding snowpack δ¹⁸O ranged from −22.25 to −6.25‰. The coefficient of variation of δ¹⁸O in snowpack levels decreased from −0.37 to −0.07 from winter to spring, indicating isotopic snowpack homogenization. Meltwater δ¹⁸O ranged from −15.30 to −8.05‰, with variations of up to 2.95‰ observed within a single snowmelt episode, highlighting the need for frequent sampling. Early snowmelt originated in the lower snowpack with higher δ¹⁸O through ground heat flux and rainfall. After the snowpack became isothermal, infiltrating snowmelt displaced the higher δ¹⁸O liquid in the lower snowpack through a piston flow process. Fractionation analysis using a two-component mixing model on the isothermal snowpack indicated that δ¹⁸O in the initial and final half of major snowmelt was 1.30‰ lower and 1.45‰ higher, respectively, than the value from simple mixing. Mean snowpack δ¹⁸O on individual profiling days showed a steady increase from −15.15 to −12.05‰ due to removal of lower δ¹⁸O snowmelt and addition of higher δ¹⁸O rainfall. Results suggest that direct sampling of snowmelt and snow cores should be undertaken to quantify tracer input compositions adequately. The snowmelt sequence also suggests that regimes of early lower δ¹⁸O and later higher δ¹⁸O melt may be modeled and used in catchment tracing studies.     

Correlated chemical and isotopic zoning in carbonates in the martian meteorite ALH84001

The meteorite ALH84001, a sample of the ancient martian crust, contains small quantities (1%) of strongly chemically zoned carbonate. High spatial resolution (10 μm) ion microprobe analyses show that the chemical zoning is strongly correlated with variations in oxygen isotope ratios. Early formed Ca,Fe-rich cores have δ¹⁸O 7‰ increasing to 22‰ SMOW in the more Mg-rich outer cores and magnesite rims. Isolated areas of ankerite appear to be isotopically lighter with δ¹⁸O 1‰. The large range in δ¹⁸O requires a significant range in either fluid isotopic composition, or temperature, or both, in the course of the deposition sequence. Our data are inconsistent with formation of the zoned carbonates by closed system Rayleigh fractionation. There is no unique interpretation of the oxygen data, but the recent observation of existence of Δ¹⁷O excesses in the carbonate appears to rule out models which involve high temperature isotopic exchange with silicate. Comparison with terrestrial analogues suggests that ALH84001 carbonates formed in a hydrothermal system with T<400°C, and which, at least in the early stages of formation, may have involved water with δ¹⁸O < 0‰ SMOW. The later stages of deposition probably occurred at temperatures below 150°C, a conclusion which does not preclude the co-existence of thermophilic bacteria; temperatures during earlier stages of deposition are less likely to have been hospitable to bacteria.     

Calibrations for benthic foraminiferal Mg/Ca paleothermometry and the carbonate ion hypothesis

Benthic foraminiferal magnesium/calcium ratios were determined on one hundred and forty core-top samples from the Atlantic Ocean, the Norwegian Sea, the Indian Ocean, the Arabian Sea and the Pacific Ocean, mostly at sites with bottom water temperatures below 5 °C. Mg/Ca ratios are consistently lower, by  0.2 mmol/mol, in samples cleaned using oxidative and reductive steps than using oxidative cleaning. Differences between Cibicidoides species have been identified: Mg/Ca of Cibicidoides robertsonianus > Cibicidoides kullenbergi > Cibicidoides wuellerstorfi. Comparison with bottom water temperatures support observations of lowered Mg/Ca of C. wuellerstorfi at temperature below  3 °C compared with values predicted by published calibrations and from other Cibicidoides species. Hydrographic data shows that carbonate ion saturation (Δ[CO₃²⁻]) decreases rapidly below this temperature. An empirical sensitivity of Δ[CO₃²⁻] on Mg/Ca has been established for C. wuellerstorfi of 0.0086 ± 0.0006 mmol/mol/μmol/kg. A novel application using modern temperatures and Last Glacial Maximum temperatures derived via pore fluid modelling supports a carbonate ion saturation state effect on Mg incorporation. This may significantly affect calculated δ¹⁸O_seawater obtained from foraminiferal δ¹⁸O and Mg/Ca temperature.     

Lithium isotope composition of ordinary and carbonaceous chondrites, and differentiated planetary bodies: Bulk solar system and solar reservoirs

In order to better constrain the Li isotope composition of the bulk solar system and Li isotope fractionation during accretion and parent body processes, Li isotope compositions and concentrations were determined on a number of meteorite falls and finds. This is the first comprehensive study that systematically investigates a representative set of samples from carbonaceous chondrites (CI, CM2, CO3, CV3, CK4 and one ungrouped member), enstatite chondrites (EH, EL), ordinary chondrites (H, L, LL), and achondrites (one eucrite, diogenites, one pallasite, and a silicate inclusion from a IAB iron).

Carbonaceous chondrites have an average isotope composition of δ⁷Li = + 3.2‰ ± 1.9 (2σ) which agrees with the average composition of relatively pristine olivines (representative for the bulk composition) from the Earth primitive upper mantle (PUM). This is lighter than the average δ⁷Li of the basaltic differentiates of the Earth, Moon and Mars and the achondrites. It is an important observation, however, that the lighter end of the isotopic range of the differentiates always coincides with the averages of the mantle olivines and the carbonaceous chondrites. From this we conclude that the bulk of the inner solar system consists mostly of material from carbonaceous chondrites and that the variation seen in the differentiates is due to planetary body processes. Ordinary chondrites are significantly lighter than carbonaceous chondrites. No significant differences in δ⁷Li exist between enstatite chondrites (n = 3) and carbonaceous or ordinary chondrites. The difference between carbonaceous and ordinary chondrites and the variability within the chondrites could indicate the existence of distinct Li isotope reservoirs in the early solar nebula.     

Fe isotope fractionation in iron meteorites: New insights into metal-sulphide segregation and planetary accretion

Magmatic iron meteorites are considered to be remnants of the metallic cores of differentiated asteroids, and may be used as analogues of planetary core formation. The Fe isotope compositions (δ^57/54Fe) of metal fractions separated from magmatic and non-magmatic iron meteorites span a total range of 0.39‰, with the δ^57/54Fe values of metal fractions separated from the IIAB irons (δ^57/54Fe 0.12 to 0.32‰) being significantly heavier than those from the IIIAB (δ^57/54Fe 0.01 to 0.15‰), IVA (δ^57/54Fe − 0.07 to 0.17‰) and IVB groups (δ^57/54Fe 0.06 to 0.14‰). The δ^57/54Fe values of troilites (FeS) separated from magmatic and non-magmatic irons range from − 0.60 to − 0.12‰, and are isotopically lighter than coexisting metal phases. No systematic relationships exist between metal-sulphide fractionation factor (Δ^57/54Fe_M-FeS = δ^57/54Fe_metal − δ^57/54Fe_FeS) metal composition or meteorite group, however the greatest Δ^57/54Fe_M-FeS values recorded for each group are strikingly similar: 0.79, 0.63, 0.76 and 0.74‰ for the IIAB, IIIAB, IAB and IIICD irons, respectively. Δ^57/54Fe_M-FeS values display a positive correlation with kamacite bandwidth, i.e. the most slowly-cooled meteorites, which should be closest to diffusive equilibrium, have the greatest Δ^57/54Fe_M-FeS values. These observations provide suggestive evidence that Fe isotopic fractionation between metal and troilite is dominated by equilibrium processes and that the maximum Δ^57/54Fe_M-FeS value recorded (0.79 ± 0.09‰) is the best estimate of the equilibrium metal-sulphide Fe isotope fractionation factor. Mass balance models using this fractionation factor in conjunction with metal δ^57/54Fe values and published Fe isotope data for pallasites can explain the relatively heavy δ^57/54Fe values of IIAB metals as a function of large amounts of S in the core of the IIAB parent body, in agreement with published experimental work. However, sequestering of isotopically light Fe into the S-bearing parts of planetary cores cannot explain published differences in the average δ^57/54Fe values of mafic rocks and meteorites derived from the Earth, Moon and Mars and 4-Vesta. The heavy δ^57/54Fe value of the Earth's mantle relative to that of Mars and 4-Vesta may reflect isotopic fractionation due to disproportionation of ferrous iron present in the proto-Earth mantle into isotopically heavy ferric iron hosted in perovskite, which is released into the magma ocean, and isotopically light native iron, which partitions into the core. This process cannot take place at significant levels on smaller planets, such as Mars, as perovskite is only stable at pressures > 23 GPa. Interestingly, the average δ^57/54Fe values of mafic terrestrial and lunar samples are very similar if the High-Ti mare basalts are excluded from the latter. If the Moon's mantle is largely derived from the impactor planet then the isotopically heavy signature of the Moon's mantle requires that the impacting planet also had a mantle with a δ^57/54Fe value heavier than that of Mars or 4-Vesta, which then implies that the impactor planet must have been greater in size than Mars.     

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely be controlled by isotope fractionation between the free and complexed iron. We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fe-desferrioxamine B (at pH 2). The two differently complexed Fe(III) pools were separated by addition of Na₂CO₃, which led to immediate precipitation of the inorganic Fe without causing significant dissociation of Fe-desferrioxamine complexes. Experiments using enriched ⁵⁷Fe tracer showed that isotopic equilibration between the ⁵⁷Fe-labelled inorganic species and the isotopically “normal” siderophore-bound Fe was rapid during the first few seconds and then became slower. Consequently, the data fitted poorly to first and second order reaction equations. However, with a two-stage reaction, the data fit perfectly with a first order equation for the slower stage, indicating that approximately 40% re-equilibration may take place during the separation of the two pools. To further test if the induced precipitation leads to experimental artefacts, the fractionation during precipitation of inorganic Fe was determined. Assuming a Rayleigh-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of ⁵⁶Fe_{solution-solid} = 1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within experimental uncertainty, yielding an average fractionation factor, Δ⁵⁶Fe_DFOB-inorg of 0.60 ± 0.15‰. The results indicate that equilibrium Fe isotope fractionation induced by strongly coordinating organic ligands may fractionate Fe isotopes in nature. The fractionation is likely to be important in oxic, Fe(III)-bearing environments, such as soils and rivers, and may, for example, largely control the Fe isotope composition of marine Fe–Mn crusts.     

Compound-specific radiocarbon dating of Ross Sea sediments: A prospect for constructing chronologies in high-latitude oceanic sediments

We present an overview of the problems relating to the development of sedimentary chronologies for Antarctic margin sediments, and review the recent application of compound-specific radiocarbon dating methods for resolving them. Radiocarbon dating of solvent-extractable, short-chain (C₁₄, C₁₆, and C₁₈) fatty acids isolated from surface sediments of the Ross Sea, Antarctica, revealed their ages to be consistent with that of the modern dissolved inorganic carbon (DIC) reservoir age (pre-bomb, Δ¹⁴C≈−150‰; post-bomb, Δ¹⁴C≈−100‰) in this region. This contrasts sharply with the radiocarbon ages of bulk organic matter in the corresponding sediments are substantially older (Δ¹⁴C=−298‰ to −712‰). Furthermore, the radiocarbon ages of these fatty acids progressively increase with the core depth. These results clearly show a utility of the compound-specific radiocarbon dating for developing sediment chronologies in the Antarctic margin sediments. This approach is potentially applicable to Arctic Ocean, as well as other areas of Southern Ocean where similar interferences by fossil or pre-aged carbon inputs have hindered the progress in the development of late Quaternary paleoceanographic records.     

Organic carbon and nitrogen stable isotopes in the intertidal sediments from the Yangtze Estuary, China

The natural isotopic compositions and C/N elemental ratios of sedimentary organic matter were determined in the intertidal flat of the Yangtze Estuary. The results showed that the ratios of carbon and nitrogen stable isotopes were respectively −29.8‰ to − 26.0‰ and 1.6‰–5.5‰ in the flood season (July), while they were −27.3‰ to − 25.6‰ and 1.7‰–7.8‰ in the dry season (February), respectively. The δ¹³C signatures were remarkably higher in July than in February, and gradually increased from the freshwater areas to the brackish areas. In contrast, there were relatively complex seasonal and spatial changes in stable nitrogen isotopes. It was also reflected that δ¹⁵N and C/N compositions had been obviously modified by organic matter diagenesis and biological processing, and could not be used to trace the sources of organic matter at the study area. In addition, it was considered that the mixing inputs of terrigenous and marine materials generally dominated sedimentary organic matter in the intertidal flat. The contribution of terrigenous inputs to sedimentary organic matter was roughly estimated according to the mixing balance model of stable carbon isotopes.     

Lithium isotope fractionation in the southern Cascadia subduction zone

We present lithium (Li) abundances and isotope compositions for a suite of anhydrous olivine tholeiites (HAOTs) and hydrous basalt-andesitic (BA) lavas from the Mt. Shasta and Medicine Lake regions, California. The values of δ⁷Li vary from + 0.9‰ to + 6.4‰ and correlate inversely with distance from the trench. These data are consistent with continuous isotope fractionation of Li during dehydration of the subducted oceanic lithosphere, an interpretation corroborated by uniformly high pre-eruptive H₂O contents in basaltic andesites accompanied by high Li, Rb, Sr, Ba and Pb abundances. The subduction-derived component that was added to these hydrous magmas is shown to be very similar beneath both Mt. Shasta and Medicine Lake volcanoes despite characteristically distinct Li isotope compositions in the magmas themselves. More evolved andesites and dacites from Mt. Shasta have δ⁷Li from + 2.8 to + 6.9‰ which is identical with the range obtained for HAOTs and BA lavas from Mt. Shasta. Therefore, Li isotopes do not provide evidence for any other crustal component admixed to Mt. Shasta andesites or dacites during magmatic differentiation and magma mixing in the crust.     

Sulfate reduction using methane in sediments beneath a bathyal “cold seep” giant clam community off Hatsushima Island, Sagami Bay, Japan

Two sandy sediment cores (Cores D227-120 and D380) were collected from inside a deep-sea giant clam (Calyptogena soyoae) community off Hatsushima Island, western Sagami Bay, central Japan (35°59.9′N, 139°13.6′E; 1160 m deep) and a muddy sediment core (Core D227-202) was obtained from outside the community by the submersibleShinkai 2000. The chloride concentration of the pore waters is constant vertically and sulfate reduction using sedimentary organic matter occurs in Core D227-202 (21 cm long). The chloride concentrations are lower by 7% at the 7.5–9 cm depth in Core D227-120 (9 cm long) and by 3% at the 11–12 cm depth in Core D380 (16 cm long) than those of the overlying bottom waters in the cores from inside of the community. Sulfate concentration decreases remarkably and dissolved inorganic carbon, alkalinity, ammonium-N, and hydrogen sulfide concentrations increase significantly with increasing depth in Core D380.δ³⁴S values of sulfate ions increase from +20.5 to +35.3‰ andδ¹³C values of dissolved inorganic carbon decrease drastically from −7.0 to −45‰ with increasing depth from the top to the bottom of the core, although theδ¹³C values of the organic carbon of the sediments are−23.7 ± 0.9‰ in Core D380. These results indicate that sulfate reduction using methane is active within the sediments just beneath the living clams and that the hydrogen sulfide produced can be used by endosymbiotic sulfur oxidizing bacteria living in the gills ofC. soyoae in the community.     

A comparison of the toluene distillation and vacuum/heat methods for extracting soil water for stable isotopic analysis

Hanford Loam, from Richland, Washington, was used as a test soil to determine the precision, accuracy and nature of two methods to extract soil water for stable isotopic analysis: azeotropic distillation using toluene, and simple heating under vacuum. The soil was oven dried, rehydrated with water of known stable isotopic compositions, and the introduced water was then extracted.

Compared with the introduced water, initial aliquots of evolved water taken during a toluene extraction were as much as 30 ‰ more depleted in D and 2.7 ‰ more depleted in ¹⁸O, whereas final aliquots were as much as 40 ‰ more enriched in D and 14.3 ‰ more enriched in ¹⁸O. Initial aliquots collected during the vacuum/heat extraction were as much as 64 ‰ more depleted in D and 8.4 ‰ more depleted in ¹⁸O than was the introduced water, whereas the final aliquots were as much as 139 ‰ more enriched in D, and 20.8 ‰ more enriched in ¹⁸O. Neither method appears quantitative; however, the difference in stable isotopic composition between the first and last aliquots of water extracted by the toluene method is less than that from the vacuum/heat method. This is attributed to the smaller fractionation factors involved with the higher average temperatures of distillation of the toluene. The average stable isotopic compositions of the extracted water varied from that of the introduced water by up to 1.4 ‰ in δD and 4.2 ‰ in δ¹⁸O with the toluene method, and by 11.0 ‰ in δD and 1.8 ‰ in δ¹⁸O for the vacuum/heat method.

The lack of accuracy of the extraction methods is thought to be due to isotopic fractionation associated with water being weakly bound (not released below 110°C) in the soil. The isotopic effect of this heat-labile water is larger at low water contents (3.6 and 5.2% water by weight) as the water bound in the soil is a commensurately larger fraction of the total. With larger soilwater contents the small volume of water bound with an associated fractionation is not enough to affect the remaining unbound introduced soil water. Pretreatment of the soil to equilibrate the heat-labile water to the test water produced good results for the toluene distillation but not the vacuum/heat extraction method.

Vapors collected over the soils also show stable isotopic variations related to soilwater content. These vapors also appear to be in closer equilibrium with the free water, as extracted by the toluene method, than with the originally introduced water; thus, the soil vapors do not appear to be isotopically affected by the heat-labile water.

The toluene method appears to be better for extracting soil water for stable isotopic analysis because it allows more precise temperature control and excludes the extraction of heat-labile water which is isotopically fractionated. The bound nature of this heat-labile water limits association with the hydrologically active soil water; thus, the exclusion of this water from the soil water attained by toluene distillation may be advantageous. However, the azeotropic nature of toluene distillation affords no benefit and the extraction procedure must continue to completion.     

A 53 year seasonally resolved oxygen and carbon isotope record from a modern Gibraltar speleothem: Reconstructed drip water and relationship to local precipitation

The response of a climate proxy against measured temperature, rainfall and atmospheric circulation patterns at sub-annual resolution is the ultimate test of proxy fidelity but very few data exist showing the level of correspondence between speleothem climate proxies and the instrumental climate record. Cave sites on the Gibraltar peninsula provide a unique opportunity to calibrate speleothem climate proxies with the longest known available precipitation isotopes and instrumental records. An actively growing speleothem sampled from New St. Michaels Cave in 2004 is composed of paired laminae consisting of light columnar calcite and a darker microsparitic calcite. Stable isotope analysis of samples micromilled in 100 μm steps at the equivalent of bi-monthly intervals reveals fabric-correlated annual cycles in carbon isotopes, oxygen isotopes and trace elements responding to seasonal changes in cave microclimate, hydrology and ventilation patterns. Calcite δ¹³C values reach a minimum in the light columnar fabric and evidence from trace element behaviour and cave monitoring indicates that this grows under cave ‘winter’ conditions of highest pCO₂, whereas the dark microsparitic calcite, characterised by elevated δ¹³C and δ¹⁸O values grows under low ‘summer’ pCO₂ conditions. Drip water δ¹³C_DIC reaches a minimum in March–April, at which time the attenuated δ¹⁸O signal becomes most representative of winter precipitation. An age model based on cycle counting and the position of the ¹⁴C bomb carbon spike yields a precisely dated winter oxygen isotope proxy of cave seepage water for comparison with the GNIP and instrumental climate record for Gibraltar. The δ¹⁸O characteristics of calcite deposited from drip water representing winter precipitation for each year can be derived from the seasonally resolved record and allows reconstruction of the δ¹⁸O drip water representing winter precipitation for each year from 1951–2004. These data show an encouraging level of correspondence (r² = 0.47) with the δ¹⁸O of rainfall falling each year between October and March and on a decadal scale the δ¹⁸O of reconstructed winter drip water mirrors secular change in mean winter temperatures.     

Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa

Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO₃²⁻], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO₃, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO₃ export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δ_sed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δ_sed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.     

Late Pleistocene to Holocene composite speleothem O and C chronologies from South Island, New Zealand—did a global Younger Dryas really exist?

Oxygen and carbon data from eight stalagmites from northwest South Island are combined to produce composite records of δ¹⁸O and δ¹³C from 23.4 ka to the present. The chronology is anchored by 43 thermal ionization mass spectrometry (TIMS) uranium series ages. Delta ¹⁸O values are interpreted as having a first order positive relationship to temperature, but also to be influenced by precipitation in a complex manner. Delta ¹³C is interpreted as responding negatively to increases in atmospheric CO₂ concentration, biological activity and precipitation amount.

Six climatic phases are recognized. After adjustment of 1.2‰ for the ice volume effect, the δ¹⁸O record between 23 and 18 ka varies around −3.72‰ compared to the Holocene average of −3.17‰. Late-glacial warming commenced between 18.2 and 17.8 ka and accelerated after 16.7 ka, culminating in a positive excursion between 14.70 and 13.53 ka. This was followed by a significant negative excursion between 13.53 and 11.14 ka of up to 0.55‰ depth that overlapped the Antarctic Cold Reversal (ACR) and spanned the Younger Dryas (YD). Positive δ¹⁸O excursions at 11.14 ka and 6.91–6.47 ka represent the warmest parts of the Holocene. The mid-Holocene from 6 to 2 ka was marked by negative excursions that coincide with increased glacial activity in the South Island. A short positive excursion from 0.71 to 0.57 ka was slightly later than the Medieval Warm Period of Europe.

Delta ¹³C values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in δ-values after 17.79 ka probably corresponds to an increase in atmospheric CO₂ concentration, biological activity and wetness at the end of the Last Glaciation, but the reversal identified in the δ¹⁸O record from 13.53 to 11.14 ka was not reflected in δ¹³C changes. The lowest δ¹³C values coincided with the early Holocene climatic suboptimum when conditions were relatively wet as well as mild.

Major trends in the δ¹⁸O_c record are similar to the Northern Hemisphere, but second order detail is often distinctly different. Consequently, at the millennial scale, a more convincing case can be made for asymmetric climatic response between the two hemispheres rather than synchronicity.     

An oxygen isotopic profile through the upper kilometer of the oceanic crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in¹⁸O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 haveδ¹⁸O values generally ranging from +6.1 to +8.5‰ SMOW(mean= +7.0‰), although minor zeolite-rich samples range up to 12.7‰. Rocks depleted in¹⁸O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6‰, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4‰, respectively.

Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10–100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios ( 1), and hydrothermal fluids probably contained mantle-derived CO₂. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient ( 2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and¹⁸O enrichment of fluids, resulting in local increases inδ¹⁸O of rocks which had been previously depleted in¹⁸O during prior axial metamorphism.