Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO₂–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (100°C) aquifer of mixed marine–meteoric water. The measured ³He/⁴He ratios and δ¹³C of both the free gases (4.5–7.3 R_a and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 R_a and −7.1 to −0.9‰), together with their covariation with the He/CO₂ ratio, constrain a ³He/⁴He ratio of 7.3±0.1 R_a and a δ¹³C of ca. −4‰ for the magmatic end-member. These latter are best preserved in fluids emanating inside the active caldera of Pantelleria, in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir. Outside the caldera, the magmatic component is more affected by air dilution and, at a few sites, by mixing with either organic carbon and/or radiogenic ⁴He leached from the U–Th-rich trachytic host rocks of the aquifer. Pantelleria magmatic end-member is richer in ³He and has a lower (closer to MORB) δ¹³C than all fluids yet analyzed in volcanic regions of Italy and southern Europe, including Mt. Etna in Sicily (6.9±0.2 R_a, δ¹³C=−3±1‰). This observation is consistent with a south to north increasing imprint of subducted crustal material in the products of Italian volcanoes, whose He and C (but also O and Sr) isotopic ratios gradually evolve towards crustal values northward of the African–Eurasian plate collision boundary. Our results for Pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or ‘less contaminated’, ³He-richer mantle source beneath the Sicily Channel rift zone. The lower than MORB ³He/⁴He ratio but higher than MORB CO₂/³He ratio of Pantelleria volatile end-member are compatible with petro-geochemical evidence that this mantle source includes an upwelling HIMU–EM1-type asthenospheric plume component whose origin, according to recent seismic data, may be in the lower mantle.     

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.     

Groundwater recharge and palaeoclimate in the Sirte and Kufra basins, Libya

Stable and radio-isotope results (C, H, O) for groundwaters from the Sirte and northern Kufra basins are used to determine the recharge history during the Holocene and late Pleistocene. Radiocarbon ages have been corrected on the basis of their stable carbon isotope ratios and on environmental samples from the areas, and two groups may be recognised: (1) low ¹⁴C activity groundwaters (13000–34000 yr. BP) with δ ¹³C-5.6 to −11.7‰; and (2) higher ¹⁴C activity groundwaters (5000–7800 yr. BP) enriched in ¹³C up to δ ¹³C = −3.2‰. There is a general correlation of age with depth.

A well defined freshwater (< 50 mg/l Cl⁻) channel can be traced within the aquifer for some 130 km through the region, which is considered to represent recharge from a former wadi. This water with an age of ± 7800 yr. BP is chemically and isotopically distinct from the regional groundwaters and provides direct evidence of a significant recharge event during the Holocene.

The stable isotope (O and H) composition of groundwater from the Kufra and Sirte basins are all related by an evaporative line with slope δ D = 4.5δ ¹³O − 35 with an intercept on the meteoric line of -11‰. This suggests a recharge source continuing into the Holocene from air masses, analogous to current heavy monsoon rain derived from south of the Sahara. The spatial and temporal distribution of groundwaters in relation to the evaporative line suggests a progressive change in character of the recharge which is controlled by a shift towards strongly convective rainfall during the Holocene.

The direct hydrogeological and geochemical evidence supports climatic models proposed by several workers in which discrete humid episodes during the Holocene are inferred.     

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.     

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.     

Bomb C time history recorded in two modern stalagmites — importance for soil organic matter dynamics and bomb C distribution over continents

Carbon 14 activity measurements made by Accelerator Mass Spectrometry on two modern stalagmites from the Han-sur-Lesse cave (Belgium) and from the Postojna Cave (Slovenia) permit the construction of ¹⁴C activity (a¹⁴C) time series over the last 50 years. A high precision chronology is given by annual laminae in the first stalagmite and by a specific mark (explosion in the Postojna Cave in 1944) in the second one. In both stalagmites, ¹⁴C activity increase due to nuclear tests in the atmosphere is remarkable. However, instead of a sharp peak like the one observed in the atmosphere around 1963–1964, the ¹⁴C activities of the stalagmite CaCO₃ show an abrupt increase, with an offset of 1–10 years, followed by a high activity plateau for the Han-sur-Lesse sample and a slight decrease for the Postojna sample. For both stalagmites, the variation of the a¹⁴C amplitude between pre- and post-bomb period is much lower than the atmospheric record, which demonstrates the damping effect of the soil carbon reservoir. We have modeled the CaCO₃ activities using fractionation processes between atmosphere CO₂, soil CO₂ and organic matter (OM), dissolved inorganic carbon and stalagmite CaCO₃. In both cases studied, the model and former soil studies suggest that CO₂ from soil organic matter (SOM) decomposition, which has a slow turnover (i.e. >1 y), is of major importance in winter, when the development of speleothem is the most important. Combined with the fact that 80–90% of the stalagmite carbon comes from soil CO₂, this produces a damping effect on the speleothem a¹⁴C. Consequently, the ‘geochemical time resolution', at least for speleothem carbon, is much lower than the structural resolution given by annual laminae alternations and is mainly controlled by soil carbon dynamics: a¹⁴C and δ¹³C are smoothed over several years. Differences between the ¹⁴C time series of the Han-sur-Lesse and Postojna stalagmites are likely to be due to the double amount of precipitation in Postojna, which produces a faster soil OM turnover and thus a ‘system' which is more sensitive to atmospheric changes.     

Ages and composition of gas trapped in Allan Hills and Byrd core ice

Gas is extracted from large (6–31 kg) Antarctic ice samples to obtain sufficient CO₂ for¹⁴C measurements with small low-level proportional counters. The¹⁴C ages of Byrd core ice are in accord with glaciological estimates ranging from (2.2_−1.1^+1.4)×10³ yr at 271 m depth to more than 8 × 10³ yr at 1071 m depth. The CO₂ abundances in gas extracted from Byrd core ice range from 0.0216 to 0.051%, with below present-day atmosphere CO₂ abundances for ice from 1068 and 1469 m depths. The CO₂ abundance in gas from Allan Hills surface ice samples ranges between four and six times the atmospheric value and the CO₂ had a specific activity three times that of contemporary carbon. A possible explanation for the anomalously high specific activity is surface melting with the incorporation into CO₂ of¹⁴C produced by cosmic ray spallation of oxygen in ice. The CO₂ abundance in gas extracted from subsurface Allan Hills ice ranged from 0.030 to 0.065%, and the specific activities are below contemporary carbon, indicating ages greater than 5×10³ yr. The¹⁸O/¹⁶O ratio of oxygen in the trapped gas is the same as that of atmospheric oxygen and differs markedly from the¹⁸O/¹⁶O ratio in the ice. The O₂, N₂, and Ar abundances and isotopic compositions are similar to those in contemporary air, except for positive¹⁵N/¹⁴N ratios in a few samples.     

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.     

U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.     

Evidence for a mantle component shown by rare gases, C and N isotopes in polycrystalline diamonds from Orapa (Botswana)

In an attempt to constrain the origin of polycrystalline diamond, combined analyses of rare gases and carbon and nitrogen isotopes were performed on six such diamonds from Orapa (Botswana). Helium shows radiogenic isotopic ratios of R/Ra = 0.14–1.29, while the neon ratios (²¹Ne/²²Ne of up to 0.0534) reflect a component from mantle, nucleogenic and atmospheric sources. ⁴⁰Ar/³⁶Ar ratios of between 477 and 6056 are consistent with this interpretation. The (¹²⁹Xe/¹³⁰Xe) isotopic ratios range between 6.54 and 6.91 and the lower values indicate an atmospheric component. The He, Ne, Ar and Xe isotopic compositions and the Xe isotopic pattern are clear evidence for a mantle component rather than a crustal one in the source of the polycrystalline diamonds from Orapa. The δ¹³C and δ¹⁵N isotopic values of − 1.04 to − 9.79‰ and + 4.5 to + 15.5‰ respectively, lie within the range of values obtained from the monocrystalline diamonds at that mine. Additionally, this work reveals that polycrystalline diamonds may not be the most appropriate samples to study if the aim is to consider the compositional evolution of rare gases through time. Our data shows that after crystallization, the polycrystalline diamonds undergo both gas loss (that is more significant for the lighter rare gases such as He and Ne) and secondary processes (such as radiogenic, nucleogenic and fissiogenic, as well as atmospheric contamination). Finally, if polycrystalline diamonds sampled an old mantle (1–3.2 Ga), the determined Xe isotopic signatures, which are similar to present MORB mantle – no fissiogenic Xe from fission of ²³⁸U being detectable – imply either that Xe isotopic ratios have not evolved within the convective mantle since diamond crystallization, or that these diamonds are actually much younger.     

Open-system degassing of sulfur from Krakatau 1883 magma

We present the first sulfur and oxygen isotopic data for tephra from the catastrophic 1883 eruption of Krakatau. Sulfur isotopic ratios in unaltered Krakatau tephra erupted August 26–27, 1883 are markedly enriched in ³⁴S relative to mantle sulfur. High δ³⁴S values of +6.3 to +16.4‰ can best be explained by open-system or multi-stage degassing of SO₂ from the oxidized rhyodacitic and gray dacitic magmas with ³⁴S enrichment of SO²⁻₄ remaining in the melt. Lower whole-rock δ³⁴S values of +2.6‰ and +4.0‰ in two oxidized gray dacitic samples indicate more primitive subarc mantle sulfur in the 1883 magma chamber. Initial δ³⁴S of the rhyodacitic magma was probably in the +1.5‰ to +4.0‰ range and similar to δ³⁴S values measured in arc volcanic rocks from the Mariana Arc.     

Hydrochemical and stable isotope evidence for the extent and nature of the effective Chalk aquifer of north Norfolk, UK

In eastern England the Chalk aquifer is covered by extensive Pleistocene deposits which influence the hydraulic conditions and hydrochemical nature of the underlying aquifer. In this study, the results of geophysical borehole logging of groundwater temperature and electrical conductivity and depth sampling for major ion concentrations and stable isotope compositions (δ¹⁸O and δ²H) are interpreted to reveal the extent and nature of the effective Chalk aquifer of north Norfolk. It is found that the Chalk aquifer can be divided into an upper region of fresh groundwater, with a Cl concentration of typically less than 100 mg l⁻¹, and a lower region of increasingly saline water. The transition between the two regions is approximately 50 m below sea-level, and results in an effective aquifer thickness of 50–60 m in the west of the area, but less than 25 m where the Eocene London Clay boundary is met in the east of the area. Hydrochemical variations in the effective aquifer are related to different hydraulic conditions developed in the Chalk. Where the Chalk is confined by low-permeability Chalky Boulder Clay, isotopically depleted groundwater (δ¹⁸O less than −7.5‰) is present, in contrast to those areas of unconfined Chalk where glacial deposits are thin or absent (δ¹⁸O about −7.0‰). The isotopically depleted groundwater is evidence for groundwater recharge during the late Pleistocene under conditions when mean surface air temperatures are estimated to have been 4.5°C cooler than at the present day, and suggests long groundwater residence times in the confined aquifer. Elevated molar Mg:Ca ratios of more than 0.2 resulting from progressive rock-water interaction in the confined aquifer also indicate long residence times. A conceptual hydrochemical model for the present situation proposes that isotopically depleted groundwater, occupying areas where confined groundwater dates from the late Pleistocene, is being slowly modified by both diffusion and downward infiltration of modem meteoric water and diffusive mixing from below with an old saline water body.     

Variation in water use efficiency and δC levels in Eucalyptus grandis clones

This study aimed to determine whether the δ¹³C levels in the foliage and twigs of four Eucalyptus grandis clones were related to their water use efficiency (WUE). This relationship has previously been demonstrated in a number of herbaceous species but not in mature trees. The study involved accurate measurements of tree trunk growth and water use over a period of 4 months, with subsequent isotopic analysis of mature foliage from the north and south side of the canopy, and young leaves from the top of the canopy.

The water use efficiencies were found to vary from 5.97 × 10⁻³ to 12.3 × 10⁻³ m³ m⁻³. Significant differences were observed between clonal-mean water use efficiencies averaged over six sampling periods. The average δ¹³C of the mature and young foliage was found to be significantly correlated with WUE. However, the correlation was weak, suggesting that the relationship between δ¹³C and WUE is more complex in trees than suggested in the literature on crop plants. It is suggested that differences between sample trees in carbon allocation and leaf-to-air vapour pressure deficits may account for the poor correlation between δ¹³C and WUE in the four E. grandis clones studied.     

Helium isotope geochemistry of mid-ocean ridge basalts from the South Atlantic

We report new helium isotope results for 49 basalt glass samples from the Mid-Atlantic Ridge between 1°N and 47°S.³He/⁴He in South Atlantic mid-ocean ridge basalts (MORB) varies between 6.5 and 9.0 R_A (R_A is the atmospheric ratio of1.39 × 10⁻⁶), encompassing the range of previously reported values for MORB erupted away from high³He/⁴He hotspots such as Iceland. He, Sr and Pb isotopes show systematic relationships along the ridge axis. The ridge axis is segmented with respect to geochemical variations, and local spike-like anomalies in³He/⁴He, Pb and Sr isotopes, and trace element ratios such as(La/Sm)_N are prevalent at the latitudes of the islands of St. Helena, Tristan da Cunha and Gough to the east of the ridge. The isotope systematics are consistent with injection beneath the ridge of mantle “blobs” enriched in radiogenic He, Pb and Sr, derived from off-axis hotspot sources. The variability in³He/⁴He along the ridge can be used to refine the hotspot source-migrating-ridge sink model.

MORB from the 2–7°S segment are systematically the least radiogenic samples found along the mid-ocean ridge system to date. Here the depleted mantle source is characterized by⁸⁷Sr/⁸⁶Sr of 0.7022, Pb isotopes close to the geochron and with²⁰⁶Pb/²⁰⁴Pb of 17.7, and³He/⁴He of 8.6–8.9 R_A. The “background contamination” of the subridge mantle, by radiogenic helium derived from off-ridge hotspots, displays a maximum between 20 and 24°S. The HePb and HeSr isotope relations along the ridge indicate that the³He/⁴He ratios are lower for the hotspot sources of St. Helena, Tristan da Cunha and Gough than for the MORB source, consistent with direct measurements of³He/⁴He ratios in the island lavas. Details of the HeSrPb isotope systematics between 12 and 22°S are consistent with early, widespread dispersion of the St. Helena plume into the asthenosphere, probably during flattening of the plume head beneath the thick lithosphere prior to continental breakup. The geographical variation in theHe/Pbratio deduced from the isotope systematics suggests only minor degassing of the plume during this stage. Subsequently, it appears that the plume component reaching the mid-Atlantic ridge was partially outgassed of He during off-ridge hotspot volcanism and related melting activity.

Overall, the similar behavior of He and Pb isotopes along the ridge indicates that the respective mantle sources have evolved under conditions which produced related He and Pb isotope variations.     

Precise Re–Os mineral isochron and Pb–Nd–Os isotope systematics of a mafic–ultramafic sill in the 2.0 Ga Onega plateau (Baltic Shield)

We present Re–Os, Sm–Nd and Pb–Pb isotope and trace element data for the Konchozero sill, a layered mafic–ultramafic intrusion in the Early Proterozoic Onega plateau, one of the oldest continental flood basalt provinces on Earth. The Sm–Nd and Pb–Pb combined mineral and whole-rock isochron ages of 1988±34 and 1985±57 Ma for the sill coincide with the age of ferropicrites from Pechenga (the Kola Peninsula). The lithostratigraphic, chemical and isotope evidence suggest the derivation of Pechenga lavas and the Onega plateau volcanics from a single mantle plume. Peridotite and gabbro whole-rock samples, and primary ulvospinel and ilmenite mineral separates from the sill yield a Re–Os isochron with a slope corresponding to an age of 1969±18 Ma, γ_Os(T) =−0.61±5.9. This age is consistent with the other isotope data, and indicates the closed-system behavior of Re and Os in the rocks. The peridotites and ulvospinel have high Os concentrations (2.5–14 ppb) and low ¹⁸⁷Re/¹⁸⁸Os ratios (0.35–1.1), thus allowing a more accurate determination of the weighted average initial ¹⁸⁷Os/¹⁸⁸Os of 0.1144±0.0019 (2σ_pop), γ_Os(T) =+0.77±1.7. This value is lower than that determined by Walker et al. (Geochim. Cosmochim. Acta 61 (1997) 3145–3160) for the Pechenga lavas (γ_Os(T) =+6.1±0.7), and implies a substantial Os-isotope heterogeneity in this ancient plume. Compared to the Onega plateau primary basalt magma, Pechenga ferropicrites are relatively enriched in iron and Ni, have lower (Nb/Th)_N ratios (2.1 vs 1.1) and less radiogenic Nd-isotope compositions (_Nd(T) = +3.1 and +1.4, respectively), but share similar low-radiogenic Pb-isotope characteristics (μ₁=8.57 and 8.60). Incorporation of small amounts (1.5%) of outer core material into the hotter central part of the plume and subsequent contamination of the Pechenga ferropicritic magmas with the 2.9 Ga Belomorian gneisses can explain the observed chemical and isotope variations in the two provinces provided that the core had <0.25 ppm of Pb.     

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.     

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.     

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO₂CO fluids in a mid-ocean ridge basalt (morb) has been measured at 1200°C, 500–1500 bar, and oxygen fugacities between NNO and NNO-4. High oxygen fugacities, and thus CO₂-rich fluids, were produced by using a starting material equilibrated at NNO, and Ag₂C₂O₄ as the fluid source. Low oxygen fugacities were achieved by using graphite capsules, and MgCO₃ as the fluid source. These graphite-saturated fluids have the lowest possibleC/O₂CO ratio for a given pressure and temperature.

Experiments were run in a rapid-quench internally heated pressure vessel. Fluid compositions were measured using a simple vacuum technique and by Raman spectroscopy of fluid inclusions. The two techniques yielded comparable results. Fourier transform micro-infrared spectroscopy was used to identify and measure concentrations of dissolved volatiles in double-polished wafers of the quenched glasses. Carbonate was the only carbon-bearing species identified. Raman spectroscopic analysis of inclusion-free areas of glass confirmed the absence of dissolved molecular CO₂, CO and carbon. The measured concentrations of dissolved CO₂ in the glasses were proportional to the fugacity of CO₂ during the experiments, calculated from the measured fluid compositions. The data were fit to the equationX_CO2^melt(ppm)= 0.492 fCO₂ (bar).

The insolubility of CO, compared to CO₂, may be related to the fact that dissolution of CO requires reduction of another species in the melt, whereas dissolution of CO₂ does not. Due to the fact that CO will be an important component of natural CO fluids at low pressures and low oxygen fugacities, equilibrium dissolved CO₂ contents will be less than calculated assuming pure CO₂ fluids, but as theC/O₂CO ratio in a pure CO fluid at fixed pressure and temperature is a direct function of oxygen fugacity, measurement of the oxygen fugacity of quenched glasses or trapped fluids in natural samples should allow saturation concentrations to be calculated. Dissolved CO₂ contents of somemorb are less than expected if they were in equilibrium with pure CO₂. These samples must, therefore, have been more reduced than average if they were fluid-saturated. Together with results from other studies of CO₂ and H₂O solubilities in basalt, the results of this study provide a comprehensive framework for modelling CO₂ solution inmorb.     

Origin and age of thermal waters in Cieplice Spa, Sudeten, Poland, inferred from isotope, chemical and noble gas data

Isotope and hydrochemical data of the thermal water system in Cieplice laskie Zdrój (Spa) indicate the existence of two subsystems that greatly differ in volume and which meet at the fault zones of a granitic horst, where they discharge at an altitude of about 340m. One of the subsystems is very small (about 4 × 10³ m³) as indicated by the tritium age of the order of 10 years and a low outflow rate. Its recharge area found from the δ¹⁸O and δD values, is about 200m above the springs, most probably on the slopes of the foothills of the Karkonosze Mountains south-southwest of the spa. The large subsystem contains water which is free of tritium and whose ¹⁴C content is from 1 to 8 pmc with δ¹³C = −8.0 to −9.2‰. The isotopic composition of this water reflects either the climatic effect (low-altitude recharge during a cooler pre-Holocene climate) or the altitude effect (recharge in the early Holocene period at about 1000m at the heights of the Karkonosze assuming that the ¹⁴C concentration is strongly reduced by exchange with calcite in veins). For the former hypothesis, the recharge area of this water is probably either at the foot of the southeastern slopes of the Kaczawa Mountains or/and at the foot of the Rudawy Janowickie Mountains, to the east of Cieplice. The noble gas temperatures are more consistent with the pre-Holocene recharge. Similarly, the ⁴He excess and ⁴⁰Ar/³⁶Ar ratio support the hypothesis of a pre-Holecene age. The constant ³He/⁴He ratio of 26 × 10⁻⁸ for highly different helium contents indicates crustal origin of helium. For the pre-Holocene age of water its volume is calculated at >- 10⁹m³ (stagnant water in micropores and mobile water in fractures) and the hydraulic conductivity of the host granite massif is estimated at about 7 × 10⁻⁸ ms⁻¹. Two outflows from this subsystem have different and variable fractions of a modern water component (bomb age), most probably originating from the bank infiltration of a nearby stream.     

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.