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.     

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.     

Carbon isotopes in submarine basalts

High-sensitivity stepped extraction reveals two isotopically distinct forms of carbon in submarine basalt glasses: an isotopically light carbon component released by combustion from 200 to 600°C and an isotopically heavy CO₂ liberated from vesicles (magmatic carbon) from 600 to 1200°C. The δ¹³C_PDB of the low release temperature carbon varies from −24 to −30‰ and is believed to be surficial organic contamination. A survey of various types of oceanic glasses demonstrates that the δ¹³C of magmatic CO₂ varies from −4.2 to −7.5‰ in mid-ocean ridge basalt (MORB), from −2.8 to −6.7‰ in glasses from Hawaii and Explorer Seamount and from −7.7 to −16.3‰ in glasses from the Scotia Sea and Mariana Trough. Magmatic CO₂ in back-arc basin basalts (BABB) is on average 5‰ lighter than equivalent CO₂ in MORB and can be explained by the mixing in the source regions for BABB magmas of juvenile (MORB-like) CO₂ with an organic carbon component from subducted pelagic sediments. It is inferred that significant amounts of pelagic carbonate carbon (δ¹³C 0‰) must be recycled into the mantle.     

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.     

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.     

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.     

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.     

Oxygen isotope geochemistry of lavas from an oceanic to continental arc transition, Kermadec–Hikurangi margin, SW Pacific

New oxygen isotope data are presented for submarine lavas erupted close to the transition between the oceanic Kermadec island arc and the continental Taupo Volcanic Zone, New Zealand. Volcanic glasses display δ¹⁸O values ranging from +5.65‰ to +5.83‰, clinopyroxenes range from +5.23‰ to +5.78‰ and olivines range from +4.83‰ to +5.47‰. Coexisting glass and phenocrysts in the lavas are in isotopic equilibrium, with one exception. Oxygen isotope ratios of back-arc lavas erupted through oceanic crust are indistinguishable from mid-ocean ridge basalts or lavas erupted in nearby back-arc settings. Although lavas from the arc front display elevated oxygen isotope ratios, the magnitude of ¹⁸O-enrichment is too great to result from recycling of subducted material alone. A single back-arc lava erupted through continental crust is also relatively ¹⁸O-rich suggesting that the most likely origin for the high δ¹⁸O signature is limited amounts of interaction between continental crust and melts derived from a mantle wedge that has been variably fluxed by recycled oxygen. The results of modelling open system behaviour in this volcanic system highlight the need for strong controls on the composition of local contaminants. Application of ‘average' crustal lithologies, as in other volcanic provinces, may lead to erroneous conclusions regarding the involvement of local basement.     

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.     

Glacial–interglacial changes in Subantarctic sea surface temperature and δO-water using foraminiferal Mg

Laboratory culturing experiments with living Globigerina bulloides indicate that Mg/Ca is primarily a function of seawater temperature and suggest that Mg/Ca of fossil specimens is an effective paleotemperature proxy. Using culturing results and a core-top Neogloboquadrina pachyderma calibration, we have estimated glacial–interglacial changes in sea surface temperature (SST) using planktonic Mg/Ca records from core RC11-120 in the Subantarctic Indian Ocean (43°S, 80°E) and core E11-2 in the Subantarctic Pacific Ocean (56°S, 115°W). Our results suggest that glacial SST was about 4°C cooler in the Subantarctic Indian Ocean and 2.5°C cooler in the Subantarctic Pacific. Comparison of SST and planktonic δ¹⁸O records indicates that changes in SST lead changes in δ¹⁸O by on average 1–3 kyr. The glacial–interglacial temperature change indicated by the Subantarctic Mg/Ca records suggests that temperature accounts for 40–60% of the foraminiferal δ¹⁸O change. We have used the Mg/Ca-based SST estimates and δ¹⁸O determinations to generate site-specific seawater δ¹⁸O records, which suggest that seawater δ¹⁸O was on average 1‰ more positive during glacial episodes compared with interglacial episodes.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

A high resolution palaeoclimatic record for the last 27,500 years in tropical West Africa from the carbon and nitrogen isotopic composition of lacustrine organic matter

Variations in the carbon and nitrogen isotopic composition of bulk organic matter in the sediments of Lake Bosumtwi, Ghana reflect climatically induced changes to the lake and the catchment flora. Cores spanning the last 27.5 kyr of sedimentation in the lake show large oscillations inδ¹³C_org PDB andδ¹⁵N_org Air. The late Pleistocene record is particularly detailed, showing changes of ca. 20‰ in carbon and ca. 10‰ in nitrogen isotopic compositions. These variations are of complex origin. Although different in magnitude, major isotopic excursions in the two records are generally in phase and reveal the occurrence of two major dry intervals at and immediately following the Last Glacial Maximum. The Allerød-Younger Dryas period also seems to have been marked by generally dry conditions in this part of tropical West Africa. Nitrogen isotopic evidence suggests that during the period 9.2–3.2 kyr the lake had an extremely stable water column, probably due to the absence of a windy or cool, dry season, or both. Regular circulation of the water column recommenced during the late Holocene and has persisted until the present day.     

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.     

Contamination of groundwater under cultivated fields in an arid environment, central Arava Valley, Israel

The purpose of this study is to obtain a better understanding of groundwater contamination processes in an arid environment (precipitation of 50 mm/year) due to cultivation. Additional aims were to study the fate of N, K, and other ions along the whole hydrological system including the soil and vadose zone, and to compare groundwater in its natural state with contaminated groundwater (through the drilling of several wells).

A combination of physical, chemical, and isotopic analyses was used to describe the hydrogeological system and the recharge trends of water and salts to the aquifers. The results indicate that intensive irrigation and fertilization substantially affected the quantity and quality of groundwater recharge. Low irrigation efficiency of about 50% contributes approximately 3.5–4 million m³/year to the hydrological system, which corresponds to 0.65 m per year of recharge in the irrigated area, by far the most significant recharge mechanism.

Two main contamination processes were identified, both linked to human activity: (1) salinization due to circulation of dissolved salts in the irrigation water itself, mainly chloride, sulfate, sodium and calcium, and (2) direct input of nitrate and potassium mainly from fertilizers.

The nitrate concentrations in a local shallow groundwater lens range between 100 and 300 mg/l and in the upper sub-aquifer are over 50 mg/l. A major source of nitrate is fertilizer N in the excess irrigation water. The isotopic compositions of δ¹⁵N–NO₃ (range of 4.9–14.8‰) imply also possible contributions from nearby sewage ponds and/or manure. Other evidence of contamination of the local groundwater lens includes high concentrations of K (20–120 mg/l) and total organic carbon (about 10 mg/l).