Pb–Nd isotopic constraints on sedimentary input into the Lesser Antilles arc system

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north–south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions.Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd–Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. [White, W.M., Dupré, B. and Vidal, P., 1985. Isotope and trace element geochemistry of sediments from the Barbados Ridge–Demerara Plain region, Atlantic Ocean. Geochimica et Cosmochimica Acta, 49: 1875–1886.] and confirm their relatively uniform isotopic compositions (i.e., ²⁰⁶Pb/²⁰⁴Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (²⁰⁶Pb/²⁰⁴Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3.The north–south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Δ8/4 values that characterize the Lesser Antilles arc.     

Re-assessing the nitrogen signal in continental margin sediments: New insights from the high northern latitudes

Organic and inorganic nitrogen and their isotopic signatures were studied in continental margin sediments off Spitsbergen. We present evidence that land-derived inorganic nitrogen strongly dilutes the particulate organic signal in coastal and fjord settings and accounts for up to 70% of the total nitrogen content. Spatial heterogeneity in inorganic nitrogen along the coast is less likely to be influenced by clay mineral assemblages or various substrates than by the supply of terrestrial organic matter (TOM) within eroded soil material into selected fjords and onto the shelf. The δ¹⁵N signal of the inorganic nitrogen (δ¹⁵N_inorg) in sediments off Spitsbergen seems to be appropriate to trace TOM supply from various climate- and ecosystem zones and elucidates the dominant transport media of terrigenous sediments to the marine realm. Moreover, we postulate that with the study of sedimentary δ¹⁵N_inorg in the Atlantic–Arctic gateway, climatically induced changes in catchment's vegetations in high northern latitudes may be reconstructed. The δ¹⁵N_org signal is primarily controlled by the availability of nitrate in the dominating ocean current systems and the corresponding degree of utilization of the nitrate pool in the euphotic zone. Not only does this new approach allow for a detailed view into the nitrogen cycle for settings with purely primary-produced organic matter supply, it also provides new insights into both the deposition of marine and terrestrial nitrogen and its ecosystem response to (paleo-) climate changes.     

Distribution and sources of sedimentary organic matter in a tropical estuary,south west coast of India (Cochin estuary): A baseline study

Surface sediments samples were collected from 9 stations of the Cochin estuary during the monsoon, post-monsoon and pre-monsoon seasons and were analyzed for grain size, total organic carbon (OC), total nitrogen (TN) and stable isotopic ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) to identify major sources of organic matter in surface sediments. Sediment grain size is found to be the key factor influencing the organic matter accumulation in surface sediments. The δ¹³C values ranges from ?27.5‰ to ?21.7‰ in surface sediments with a gradual increase from inner part of the estuary to the seaward side that suggest an increasing contribution of marine autogenous organic matter towards the seaward side. The δ¹⁵N value varies between 3.1‰ and 6.7‰ and it exhibits complex spatial and seasonal distributions in the study area. It is found that the dynamic cycling of nitrogen through various biogeochemical and organic matter degradation processes modifies the OC/TN ratios and δ¹⁵N to a considerable degree. The fraction of terrestrial organic matter in the total organic matter pool ranges from 13% to 74% in the surface sediments as estimated by δ¹³C based two end member mixing model.     

The case for a martian origin of the shergottites: nitrogen and noble gases in EETA 79001

Nitrogen and noble gases were measured in samples of a glass inclusion and the surrounding basaltic matrix from the antarctic shergottite EETA 79001. A nitrogen component trapped in the glass, but not present in the matrix, has a δ¹⁵N value at least as high as +190‰. Ratios of⁴⁰Ar/¹⁴N and¹⁵N/¹⁴N in the glass are consistent with dilution of a martian atmospheric component (δ¹⁵N = 620 ± 160‰,⁴⁰Ar/¹⁴N= 0.33 ± 0.03) by either terrestrial atmosphere adsorbed on the samples or by indigenous nitrogen from the minerals of the rock. Trapped noble gases in the glass reproduce, within error, the elemental and isotopic compositions measured in Mars' atmosphere by Viking, and are in general agreement with previous measurements except for much lower abundances of neutron-generated krypton and xenon isotopes. The most reasonable explanation at the present time for the noble gas pattern and the isotopically heavy nitrogen is that a sample of martian atmosphere has been trapped in the EETA 79001 glass, and that this meteorite, and thus the shergottites and probably the nakhlites and chassignites as well, originated on Mars.Nitrogen in the non-glassy matrix of EETA 79001 amounts to less than 0.5 ppm and has a spallation-corrected δ¹⁵N value in the range 0 to ?20‰; it may reflect indigenous nitrogen in the basalt or a mixture of indigenous and adsorbed terrestrial nitrogen. Spallogenic noble gases yield single-stage exposure ages between 400,000 and 900,000 years, depending on irradiation geometry. Trapped argon may have an unusually low³⁶Ar/³⁸Ar ratio. Trapped krypton, except for a small excess at⁸⁰Kr, is smoothly mass-fractionated with respect to either terrestrial or chondritic Kr. The trapped xenon composition is consistent with addition of neutron-capture, radiogenic and fissiogenic isotopes to a base composition resembling terrestrial atmospheric Xe. The elemental⁸⁴Kr/¹³²Xe ratio of 25 is close to the terrestrial value and very different from the chondritic ratio.     

Elemental and stable isotope variations of organic matter from a terrestrial sequence containing the Cretaceous/Tertiary boundary at York Canyon,New Mexico

Elemental and isotopic composition of organic matter from a terrestrial sequence including the palynological Cretaceous/Tertiary (K-T) boundary together with an Ir anomaly at York Canyon, New Mexico, record information about paleoclimatological and environmental conditions. Six layers of coal, carbonaceous shale and mudstone with high contents of organic material were selected for analysis. A Late Cretaceous coal bed 10 m below the K-T boundary and an Early Tertiary coal bed containing the K-T iridium anomaly at its base were sampled intensively. In the lower bed, the isotopic ratios¹³C/¹²C,¹⁵N/¹⁴N,andD/H and the elemental ratiosC/N andN/H, all varied sympathetically with one another over depth. In contrast, in the upper coal layer, only theD/H,C/N,andN/H ratios showed some coupling. Immediately above the K-T boundary, theδ¹³C values displayed a long-term shift of 1.8‰ to more negative values, while the hydrogen isotope ratios in these samples did not change significantly. We interpret the covariations in both coal layers as sympathetic responses of the isotopic and elemental ratios to climatic and environmental changes, as have been observed for younger sedimentary organic matter. The long-termδ¹³C shift during the early Tertiary is similar to the trend observed forδ¹³C values of marine carbonates. Our data thus support the proposal that the carbon cycle was perturbed globally by the effects of a drastically decreased marine bioproductivity along the K-T transition. The uncoupling of variations in the climatically sensitive isotopic and elemental ratios seen in the Early Tertiary coal bed provides evidence for major geochemical and environmental changes in the York Canyon area at the end of the Mesozoic. On the other hand, the constancy of δD values in the organic matter deposited at and above the K-T boundary gives no indication of significant changes in the hydrologic/climatic regimes as recorded in theD/H ratios at the site for several thousand years following the event which produced the high Ir concentrations. Our results provide constraints on models that have been advanced to explain that event and its consequences.     

Nitrogen isotopic geochemical characteristics of crude oils in several basins of China

Nitrogen occupies a high content in crust and in atmospheric circle. It is one of the main elements in organism and an important element in sedimentary circle. Although nitrogen is little in crude oil, to a cer-tain degree, it influences the physical and chemical properties of oil, such as viscosity and density[1]. In reservoir the nitrogen-bearing compounds can form ion bonds or hydrogen bonds with substances on rock and form van der Vaals’ force among moleculae so they affect and alter the …     

Stable isotopes of helium, nitrogen and carbon in a coastal submarine hydrothermal system

Geothermal gases from submarine and subaerial hot springs in Ensenada, Baja California Norte, Mexico, were sampled for determination of gas chemistry and helium, nitrogen and stable carbon isotope composition. The submarine hot spring gas is primarily nitrogen (56.1% by volume) and methane (43.5% by volume), whereas nearby subaerial hot spring gases are predominantly nitrogen (95–99% by volume). The N₂/Ar ratios and σ ¹⁵N values of the subaerial hot spring gas indicate that it is atmospheric air, depleted in oxygen and enriched in helium. The submarine hot spring gas is most probably derived from marine sediments of Cretaceous age rich in organic matter. CH₄ is a major component of the gas mixture (σ ¹³C = −44.05%₀), with only minor amounts of CO₂ (σ¹³C= −10.46%₀). The σ¹⁵N of N₂ is + 0.2%₀ with a very high N₂/Ar ratio of 160. The calculated isotopic equilibra tion temperature for CH₄---CO₂ carbon exchange at depth in the Punta Banda submarine geothermal field is approximately 200°C in agreement with other geothermometry estimates. The ³He/⁴He ratios of the hot spring gases range from 0.3 to 0.6 times the atmospheric ratio, indicating that helium is predominantly derived from the radioactive decay of U and Th within the continental crust. Thus, not all submarine hydrothermal systems are effective vehicles for mantle degassing of primordial helium.     

Tracing sewage and natural freshwater input in a Northwest Mediterranean bay: Evidence obtained from isotopic ratios in marine organisms

Elemental carbon and nitrogen levels and isotope ratios were assessed in different biological compartments of a Northwest (NW) Mediterranean bay to trace the various sources of nutrient input from natural (river runoffs) and anthropogenic (harbor outflows, fish farms and urban sewage outfall) sources. Samples from transplanted mussels and natural sea grass communities (Posidonia oceanica leaves and epiphytes) were harvested from different locations throughout the bay during the touristic summer and rainy seasons. The results from the nitrogen analysis revealed that sewage and harbor outflow promote higher nitrogen levels, enrichment of ¹⁵N in the tissues, and a higher seasonal variability in sea grass and epiphytes. In mussel tissues, the δ¹⁵N was also influenced by sewage and harbor outflow, whereas δ¹³C was influenced by terrestrial inputs. These results suggest that natural and anthropogenic nutrient inputs have a temporary and localized influence and affect the sensitivity of natural isotopic ratios to changes in hydrologic conditions, especially to rain and tourism.     

Comparison of C and N stable isotope ratios between surface particulate organic matter and microphytoplankton in the Gulf of Lions (NW Mediterranean)

Carbon and nitrogen stable isotope ratios of particulate organic matter (POM) in surface water and 63–200 μm-sized microphytoplankton collected at the fluorescence maximum were studied in four sites in the Gulf of Lions (NW Mediterranean), a marine area influenced by the Rhone River inputs, in May and November 2004. Some environmental (temperature, salinity) and biological (POM, Chlorophyll a and phaeopigments contents, phytoplankton biomass and composition) parameters were also analysed. Significantly different C and N isotopic signatures between surface water POM and microphytoplankton were recorded in all sites and seasons. Surface water POM presented systematically lower δ¹³C (∼4.2‰) and higher δ¹⁵N (∼2.8‰) values than those of microphytoplankton, due to a higher content of continental and detrital material. Seasonal variations were observed for all environmental and biological parameters, except salinity. Water temperature was lower in May than in November, the fluorescence maximum was located deeper and the Chlorophyll a content and the phytoplankton biomass were higher, along with low PON/Chl a ratio, corresponding to spring bloom conditions. At all sites and seasons, diatoms dominated the phytoplankton community in abundance, whereas dinoflagellate importance increased in autumn particularly in coastal sites. C and N isotopic signatures of phytoplankton did not vary with season. However, the δ¹⁵N of surface water POM was significantly higher in November than in May in all sites likely in relation to an increase in ¹⁵N/¹⁴N ratio of the Rhone River POM which influenced surface water in the Gulf of Lions. As it is important to determine true baseline values of primary producers for analysing marine food webs, this study demonstrated that C and N isotopic values of surface water POM cannot be used as phytoplankton proxy in coastal areas submitted to high river inputs.     

Nitrogen isotope geochemistry of basaltic glasses: implications for mantle degassing and structure?

The nitrogen isotope geochemistry of 15 basaltic glasses has been investigated using stepped heating and high sensitivity static vacuum mass spectrometry. At low temperature (< 600°C) the glasses release small amounts of nitrogen with δ¹⁵N_AIR, averaging −0.3‰, suggesting surficial adsorption of atmospheric nitrogen. At high temperature, usually with a maximum at 1000°C, indigenous nitrogen with a concentration ranging from 0.2 to 2.1 ppm is released. The δ¹⁵N values of this high temperature release show a wide range from −4.5‰ to +15.5‰. There is no correlation between N ppm and δ¹⁵N, and the samples apparently form 3 groups with distinctive δ¹⁵N. Six MORB glasses from the Mid-Atlantic Ridge, East Pacific Rise and Juan de Fuca Ridge define a group with δ¹⁵N = +7.5 ± 1.3‰. In contrast two Indian Ocean MORB glasses (Carlsberg Ridge and Gulf of Aden) gave negative δ¹⁵N averaging −3.2‰. Glasses from Loihi Seamount have high δ¹⁵N averaging +14.0 ± 1.0‰. Comparison of the δ¹⁵N data with the mantle models derived from helium and argon isotope studies suggests that the wide range in δ¹⁵N may reflect in part heterogeneities in the mantle related to its degassing history. It is possible, however, that magmatic degassing processes have also affected nitrogen isotopic compositions, and the data cannot yet be unambiguously interpreted in terms of source variations.     

Organic biomarkers for tracing carbon cycling in the Gulf of Papua (Papua New Guinea)

Sediment traps were deployed in the Gulf of Papua in June–July 1997, to determine fluxes of organic matter and inorganic elements from the photic zone to deeper waters at the base of the continental slope and in the northern Coral Sea. Three stations, ranging from 900 to 1500 m depth, had “shallow” traps at 300 m below the water surface and “deep” traps set 100 m above the bottom. Infiltrex II water samplers collected particulate and dissolved organic matter from the Fly, Purari and Kikori rivers, and near-surface water from the shelf of the Gulf of Papua. Samples were analysed for molecular organic biomarkers to estimate the sources of organic carbon and its cycling processes.Dry weight fluxes from the shallow traps ranged from 115 to 181 mg m⁻² day⁻¹ and particulate organic carbon (POC) fluxes ranged from 1.2 to 1.9 mM OC m⁻² d⁻¹ with molar organic carbon to particulate nitrogen ratios (C/N) ranging from 6.0 to 6.5. Fluxes in deep traps were likely influenced by both early diagenesis and entrapment of resuspended shelf sediments. Dry weight fluxes in deep traps ranged from 106 to 574 mg m⁻² day⁻¹ and POC fluxes ranged from 0.6 to 1.5 mM OC m⁻² d⁻¹, with C/N ratios ranging from 8.5 to 10.8. ¹³C/¹²C ratios were −20.2‰ to −21.7‰ in all trap samples, indicating that most of the settling POC was “marine-derived”. Shallow traps had δ¹⁵N values of 6.3‰ to 7.2‰ while the values in deep traps were 4.9–5.0‰, indicating the N-rich near-surface OC was less degraded than that in the deep traps. The biogenic lipids consisted of hydrocarbon, sterol and fatty acid biomarkers indicative of marine zooplankton, phytoplankton and bacteria. Sterol markers for diatoms and dinoflagellates were abundant in the water samples. Highly branched isoprenoid alkenes, usually attributable to diatoms, were also detected in both water and shallow traps. Traces of C₂₆–C₃₄ n-alcohols indicative of land–plant biomarkers, were found in river water samples and in the shallow sediment traps. A large unresolved complex mixture (UCM) of hydrocarbons, and a uniform distribution of n-alkanes, indicative of petroleum hydrocarbons, were also detected in the traps. Hopane and sterane biomarkers detected in the trap oil were characteristic of a marine carbonate source, and the aromatic hydrocarbon composition distinguished at least two different oil signatures.We concluded that mass and POC fluxes were similar to those reported for other continental shelves and marginal oceans in tropical and subtropical regions. There was a dramatic decrease in POC as particles sank, due to zooplankton repackaging and photochemical and bacterial decomposition. Carbon isotopic and biomarker patterns showed most of the POC in the sediment traps was marine-sourced with only traces of terrestrial input. There was a significant flux of petroleum, which may signal the existence of natural petroleum seeps in this region.     

Distribution and composition of organic matter in surface sediments of coastal Southeast Alaska

Total organic carbon (TOC) and biogenic silica (opal) content, elemental (C/N) and isotopic (δ¹³C, δ¹⁵N) composition of organic matter and the content of lipid biomarkers derived from both marine and terrestrial sources constrain relative contributions from marine productivity and continental erosion to surface sediments throughout coastal SE Alaska (54°N to 61°N). TOC and opal content are very high (up to 8% and 33% by weight, respectively) in fjords and inlets south of Icy Strait (∼58°N) and uniformly low at offshore sites to the south, and at both offshore and inland sites to the north (averaging 0.6±0.3% and 2.3±1.8%, respectively). TOC and opal mass accumulation rates (MARs, based on bulk density and ²¹⁰Pb-derived sediment MAR) suggest dilution with terrigenous, inorganic detrital materials accounts for the low concentrations of both biogenic phases in sediments from the glacial tidewater fjords of Muir and Yakutat Bays but not elsewhere. C/N, δ¹³C, and δ¹⁵N indicate a dominant marine origin for organic matter deposited at most sites. This conclusion implicates elevated primary productivity in inland waters to the south with diatoms, based on opal results, being the dominant contributor. A very significant terrestrial organic fraction (25–50%) is contained in sediments deposited on the continental shelf to the north of 58°N. Hydrocarbon biomarkers indicate the terrestrial fraction in sediments from this region is represented by old organic matter (kerogen) likely contained within riverborne particles eroding from now heavily glaciated adjacent landscapes. In sediment to the south, the terrestrial fraction is traced to modern soil organic matter eroded from the now non-glaciated, heavily forested adjacent landscape. Our study provides a framework to guide future investigations of short- (anthropogenic) to long- (Holocene) term environmental and/or climate change in this region through down-core, stratigraphic analysis.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

Evolution of Atlantic-Pacific δC gradients over the last 2.5 m.y.

The evolution of interocean carbon isotopic gradients over the last 2.5 m.y. is examined using high-resolution δ¹³C records from deep sea cores in the Atlantic and Pacific Oceans. Over much of the Northern Hemisphere ice ages, relative reductions in North Atlantic Deep Water production occur during ice maxima. From 2.5 to 1.5 Ma, glacial reductions in NADW are less than those observed in the late Pleistocene. Glacial suppression of NADW intensified after 1.5 Ma, earlier than the transition to larger ice sheets around 0.7 Ma. At a number of times during the Pleistocene, δ¹³C values at DSDP Site 607 in the North Atlantic were indistinguishable from eastern equatorial Pacific δ¹³C values from approximately the same depth (ODP Site 677), indicating significant incursions of low δ¹³C water into the deep North Atlantic. Atlantic/Pacific δ¹³C values converge during glaciations between 1.13-1.05 m.y., 0.83-0.70 m.y., and 0.46-0.43 m.y. This represents a pseudo-periodicity of approximately 300 kyr which cannot easily be ascribed to global ice volume or orbital forcing. This partial decoupling, at low frequencies, of the δ¹⁸O and δ¹³C signals at Site 607 indicates that variations in North Atlantic deep water circulation cannot be viewed simply as a linear response to ice sheet forcing.     

Numerical models for diagenesis and the Neogene Sr isotopic evolution of seawater from DSDP Site 590B

A numerical model for the diagenetic exchange of Sr between carbonates and their pore fluids during sedimentation and compaction has been developed. The model has been applied to data from DSDP Site 590B in order to assess the accuracy with which the Sr isotope record in the carbonate sediment reflects that of seawater. The most important process affecting the Sr in the solid carbonate is exchange with the pore fluid due to solution-reprecipitation, but the concentration or isotopic composition of Sr in the solid itself gives little or no information as to the magnitude of this exchange. The key to determining the rate of exchange is the pore fluid, where the variations of Sr²⁺ and⁸⁷Sr/⁸⁶Sr with depth are very sensitive indicators. The logical structure of applying the model to data from DSDP 590B is to find by successive iteration an ocean history (i.e., the initial⁸⁷Sr/⁸⁶Sr and Sr concentration of each increment of carbonate deposited) and a rate of Sr exchange between pore water and solid carbonate such that the model matches the present Sr concentration and⁸⁷Sr/⁸⁶Sr of both pore water and solid carbonate.Once all the data are matched, the model provides an estimate of the rate of Sr exchange due to solution-reprecipitation and the evolution of⁸⁷Sr/⁸⁶Sr in seawater over the past 20 million years. For DSDP 590B we find that solution-reprecipitation decreases rapidly with depth, from a near surface value of about 10% per million years to about 1% per million years below 200 m. This rate of exchange of Sr results in the carbonates of DSDP 590B preserving an accurate record of the Sr isotopic evolution of the ocean over the past 5 million years, but for ages greater than 5 million years the⁸⁷Sr/⁸⁶Sr ratio of the carbonate is systematically displaced from that of the seawater in which it was deposited. The maximum difference is of order 5 × 10⁻⁵.     

Shifts in isotopic signatures of animals with complex life-cycles can complicate conclusions on cross-boundary trophic links

Stable isotopes (¹³C and ¹⁵N) are widely applied in studies of trophic links. We used this method to investigate the contribution of aquatic and terrestrial prey to the diet of riparian predatory arthropods in two mountain headwater streams in Colorado, USA. Aquatic and terrestrial prey and riparian predators were collected during summer 2009. To evaluate the reliability of conclusions based on stable isotope ratios, we compared the isotopic signatures of aquatic larval and terrestrial adult stages of three abundant stream insect species and assessed variation in mixing model estimates for spider diet composition under varying assumptions for trophic fractionation. Adult isotopic signatures of some aquatic prey species were indistinguishable from those of prey species with exclusively terrestrial life histories (stoneflies: ¹³C and ¹⁵N, chironomids: ¹³C). Other prey had distinctly aquatic isotopic signatures as both larvae and adults (a mayfly and a caddisfly). There was no evidence that prey with aquatic isotopic signatures contributed to the diet of the spiders near one stream. For the other stream, mixing model analysis suggested that chironomids were included in the diets of lycosid, linyphiid and liocranid spiders. Reliable estimates of the contributions of prey sources were compromised by the sensitivity of mixing models to assumptions on trophic fractionation and the presence of “isotopically cryptic” prey. This study emphasizes the importance of supporting isotope-based studies on cross-boundary trophic links with data on isotopic shifts in prey with complex life cycles and assessment of fractionation rates specific to the study system.     

The case for a martian origin of the shergottites, II. Trapped and indigenous gas components in EETA 79001 glass

Analysis of nitrogen and light noble gases in a large sample of glass (lithology C) from the antarctic shergottite EETA 79001 yields a minimumδ¹⁵N > +300‰ for the isotopic composition of nitrogen trapped in the glass. The new data fall on the mixing line through the martian atmospheric composition defined byδ¹⁵N vs.⁴⁰Ar/¹⁴N for two smaller samples analyzed previously. The results from all three samples are consistent with a two-component nitrogen system in which 84 ppb of trapped martian atmospheric N is mixed in variable proportions with another, more thermally labile N component during stepped heating. This second component, which appears to be indigenous to the glass rather than adsorbed from air and is present in amounts that vary by more than a factor of 3 from sample to sample, may represent volatiles from the martian interior. Data from crystalline phases of several SNC meteorites indicate that the indigenous gas may haveδ¹⁵N < −35‰ and³⁶Ar/¹⁴N 3 × 10⁻⁶, similar to the enstatite chondrites.Neon compositions in EETA 79001 glass samples suggest an earth-like value of 10.1 ± 0.7 for the unknown²⁰Ne/²²Ne ratio in the martian atmosphere. The nitrogen-argon correlation systematics yield trapped⁴⁰Ar/³⁶Ar= 2260 ± 200, within error of the Viking value. There is evidence that³⁶Ar/³⁸Ar in the martian atmosphere is4.1 ± 0.2, strikingly different from terrestrial or typical chondritic ratios near 5.3. Attribution of this low value to excess³⁸Ar generated over martian history by galactic cosmic-ray (GCR) spallation of surface materials would be difficult for a number of reasons, among them the excessive GCR fluences required and the absence of a corresponding²¹Ne excess.     

Compositions of deep-sea ash layers derived from north pacific volcanic arcs: variations in time and space

Glass separates from 115 ash layers derived from the Kamchatkan (DSDP Site 192; 34 layers), the eastern Aleutian (DSDP Site 183; 56 layers) and the Alaska Peninsula (DSDP Site 178; 25 layers) volcanic arcs have been analyzed for up to 28 elements. In addition, the abundance and diversity of associated mafic phenocrysts have been evaluated. The resulting data set has made possible an evaluation of the late Miocene to Recent changes in composition of ashes derived from North Pacific volcanic arcs and of the factors controlling the evolution of highly siliceous magmas.We find no evidence for a general transition from arc tholeiite to calc-alkalic magma parentage of ashes derived from the volcanic arcs during the last 10 m.y., but instead find 0.1- to 0.5-m.y. intervals during which particular types of volcanism are prevalent. Most convincing is the transition from arc tholeiite to calc-alkalic for ashes derived from Kamchatka during the last 0.8 m.y., a change believed to be associated with a landward shift in the site of magma generation. Considered together, ashes derived from North Pacific volcanic arcs have been becoming more siliceous during the last 1.5 m.y. and may be associated with accelerated subduction during the same time interval.Hydrous phenocrysts (e.g., biotite) are typically associated with low-silica deep-sea ashes, but not with terrestrial volcanic rocks of comparable silica contents, suggesting the important role of water in the evolution of siliceous magma. REE patterns and relative abundances of mafic phenocrysts demonstrate the importance of fractional crystallization in controlling the evolution of highly siliceous arc magmas. REE increase with increasing silica, but become less concentrated in ashes with SiO₂ > 64%. Eu anomalies increase throughout the SiO₂ range. Initial fractionation is dominated by clinopyroxene and plagioclase with amphibole strongly influencing fractionation above 64% SiO₂.     

Geochemistry of basalts from the Dumisseau Formation, southern Haiti: implications for the origin of the Caribbean Sea crust

Basalt and diabase from the Cretaceous Dumisseau Formation, southern Haiti have Mg-numbers of 43–63, TiO₂ contents of 1.6–3.9% and La abundances of 3.6–15.3 ppm.La/Ta ratios average 10, and indicate that the basalts are oceanic in character, distinct from the arc associations forming the northern part of Haiti. Oldest lavas have low TiO₂ (1.6%) and are LREE-depleted, similar to N-MORBs, whereas overlying lavas have higher TiO₂ (2–3.9%) and are LREE-enriched, similar to E-MORBs or hotspot basalts.⁸⁷Sr⁸⁶Sr ratios vary from 0.70280 to 0.70316,¹⁴³Nd¹⁴⁴Nd from 0.512929 to 0.513121, and²⁰⁶Pb²⁰⁴Pb from 19.00 to 19.27. LREE-depleted lavas have high¹⁴³Nd¹⁴⁴Nd (0.51309–0.51310) typical of MORBs, whereas¹⁴³Nd¹⁴⁴Nd in the LREE-enriched lavas varies widely (0.512929–0.513121).Chemical features of the Dumisseau basalts are equivalent to those of Caribbean seafloor basalts recovered on DSDP Leg 15, and support the contention that the Dumisseau is an uplifted section of Caribbean Sea crust. Oldest lavas are analogous to MORB-like basalts cored at Leg 15 Sites 146, 150, 152 and 153, and the overlying lavas are analogous to incompatible-element-enriched basalts cored at Site 151 on the Beata Ridge. Isotopic compositions of the Dumisseau basalts overlap with those of the eastern Pacific Galapagos and Easter Island hotspots. However, the presence of N-MORB basalts in the lower part of the Dumisseau and at the majority of Leg 15 Sites indicates that the anomalously thick Caribbean crust probably did not originate as a hotspot-related basaltic plateau, but may have been generated by on-ridge or near-ridge hotspot magmatism.