A discontinuous climatic record from 187 to 74 ka from a speleothem of the Clamouse Cave (south of France)

This study presents a continental paleoclimatic record in the south of France, based on δ¹⁸O, δ¹³C and the ²³⁴U/²³⁸U activity ratio, dated by the ²³⁰Th/²³⁴U disequilibrium method with thermal ionization mass spectrometry. A stalagmite (Cla4) from the Clamouse Cave offers a discontinuous stable isotopic record between 189 ka and 74 ka which covers marine isotope stages (MIS) 7, 6.4, 5.5, 5.3 and 5.1. The growth phases of the Cla4 stalagmite correspond to high sea level stages, except during MIS 6.4 (169-162 ka). All the growth phases of Cla4 correspond to humid periods, corresponding to the sapropel events observed in the eastern Mediterranean basin. Thus, the influence of a strong hydrological activity in the eastern Mediterranean basin during these periods prevailed as far west as the south of France. Because the karstic system studied strongly buffers the isotopic composition of water, isotopic variations of the calcite deposited in the cave represent mainly global and large-scale environmental variations when isotopic equilibrium conditions prevailed for calcite crystallization. Sub-stage 5.3, the end of 5.5 and MIS 7 were colder by about 4-6°C (calculated temperature) compared to present-day temperature while the growth phases of sub-stages 5.1 and the beginning of 5.5 reflect environmental conditions close to present ones. The δ¹⁸O and δ¹³C values of cave deposits of the sub-stage 6.4 are: (1) strongly marked by kinetic fractionation processes such as evaporation due to moisture deficit within the cave atmosphere during the first step of this growth phase and (2) related to higher humidity due to a second period of enhanced rainfall during the second step of growth. This study shows that even if calcite has not been deposited at isotopic equilibrium, its isotopic composition can give insights into the environmental conditions at the time of deposition.     

An isotopic calibration study of precipitation,cave dripwater,and climate in west‐central Florida

A calibration study of oxygen and hydrogen isotopic composition from precipitation and cave dripwater was conducted in west‐central Florida at Legend Cave during 2007–2008. This study was performed to better understand how modern precipitation patterns can be discerned through examination of cave dripwater and speleothem calcite for paleoclimate reconstruction. The ‘amount effect’ was shown to be a dominant control on the oxygen isotopic composition of precipitation for the study area. A meteoric water line with a slope of 6·7 suggests evaporative effects occur either during precipitation or subsequent hydrological processes. However, δ¹⁸O values of cave dripwater averaged near the mean annual amount‐weighted average of precipitation, suggesting that the isotopic composition of dripwater tracks the long‐term average of rainfall. An observed weak seasonal influence occurred in the d‐excess values, with summer precipitation being more enriched due to increased evaporative effects. Comparison of precipitation δ¹⁸O values to synoptic weather data shows the dominant amount effect influence occurs due to strong convective storms producing highly ¹⁸O‐depleted rainfall at greater amounts during the year. Constant δ¹⁸O values of the dripwater indicate that paleoclimate reconstructions using speleothems from this area would record changes in annual to interannual shifts in precipitation amount above the cave. Copyright © 2011 John Wiley & Sons, Ltd.     

Molecular and isotopic characterization of the particulate organic matter from an eutrophic coastal bay in SE Brazil

The present work aimed at studying the origin of particulate organic matter in Guanabara Bay and in some rivers of the Guanabara basin by using elemental composition, isotopic ratios (δ¹³C and δ¹⁵N) and molecular markers (sterols) in samples collected in two periods (winter and summer). Elemental and isotopic compositions were determined by dry combustion and mass spectrometry, respectively, while sterols were investigated by GC–FID and GC–MS. Higher sterol concentrations were present in the north-western part of the bay in winter (5.10–23.5 μg L^–1). The high abundance of algal sterols (26–57% of total sterols), the elemental composition (C/N=6–8) and the isotopic signatures (δ¹³C=−21.3‰ to −15.1‰ and δ¹⁵N=+7.3‰ to +11.1‰) suggested the predominance of autochthonous organic matter, as expected for an eutrophic bay, although seasonal variation in phytoplankton activity was observed. Coprostanol concentration (fecal sterol) was at least one order of magnitude higher in the particulate material from fluvial samples (4.65–55.98 μg L^–1) than in the bay waters (<0.33 μg L^–1). This could be ascribed to a combination of factors including efficient particle removal to sediments in the estuarine transition zone, dilution with bay water and bacterial degradation during particle transport in the water column.     

δO of carbonate, quartz and phosphate from belemnite guards: implications for the isotopic record of old fossils and the isotopic composition of ancient seawater

Belemnite guards of Cretaceous and Jurassic age were found to contain varying amounts of quartz deposited both on the external surface and inside the rostrum. The oxygen isotopic composition of coexisting carbonate, quartz and phosphate from the same rostrum was measured according to well-established techniques. None of these compounds showed isotopic values in equilibrium with one another. Assuming δ¹⁸O values of the diagenetic water within the range of meteoric waters, the δ¹⁸O(SiO₂) yield temperatures in agreement with the apparent secondary origin of this phase. The δ¹⁸O(CO₃²⁻) range, with a certain continuity, between −10.8 and +0.97 PDB-1 with most of the intermediate values being within the range of the carbonate isotopic values of Mesozoic fossils. The most positive isotopic results obtained from phosphate are close to +23/+24‰ (V-SMOW). They can hardly be related to a secondary origin of the phosphate, or to the presence of diagenetic effects, since these results are among the most positive ever measured on phosphate. As far as we know there is no widespread diagenetic process determining an ¹⁸O enrichment of phosphate. The very low concentration of phosphate did not allow the determination of its mineralogical composition. All the available δ¹⁸O(PO₄³⁻) values from belemnite and non-belemnite fossils of marine origin of Tertiary and Mesozoic age are reported along with the newly measured belemnites. The following conclusions may be drawn from the data reported: (1) the pristine oxygen isotope composition of fossil marine organisms (either carbonate or phosphate) may easily undergo fairly large changes because of oxygen isotope exchange processes with diagenetic water; this process is apparent even in the case of geologically recent fossils; (2) the δ¹⁸O(PO₄³⁻) of belemnite rostra seems to be, at least in the case of the most positive results, in isotopic equilibrium with environmental water because of the similarity between the results from Cretaceous belemnites and the results from Cretaceous and Lower Tertiary pelecypods and fish teeth; 3) if so, the only feasible interpretation that can be suggested for the ¹⁸O enriched data is the possibility of a relatively large variation of the oxygen isotopic composition of ocean paleowater from Jurassic to recent time.     

Evidence for a hypogene paleohydrogeological event at the prospective nuclear waste disposal site Yucca Mountain,Nevada, USA,revealed by the isotope composition of fluid-inclusion water

Secondary calcite residing in open cavities in the unsaturated zone of Yucca Mountain has long been interpreted as the result of downward infiltration of meteoric water through open fractures. In order to obtain information on the isotopic composition (δD and δ¹⁸O) of the mineral-forming water we studied fluid inclusions from this calcite. Water was extracted from inclusions by heated crushing and the δD values were measured using a continuous-flow isotope-ratio mass spectrometry method. The δ¹⁸O values were calculated from the δ¹⁸O values of the host calcite assuming isotopic equilibrium at the temperature of formation determined by fluid-inclusion microthermometry.The δD values measured in all samples range between ? 110 and ? 90‰, similar to Holocene meteoric water. Coupled δ¹⁸O–δD values plot significantly, 2 to 8‰, to the right of the meteoric water line. Among the various processes operating at the topographic surface and/or in the unsaturated zone only two processes, evaporation and water–rock exchange, could alter the isotope composition of percolating water. Our analysis indicates, however, that none of these processes could produce the observed large positive δ¹⁸O-shifts. The latter require isotopic interaction between mineral-forming fluid and host rock at elevated temperature (>100 °C), which is only possible in the deep-seated hydrothermal environment. The stable isotope data are difficult to reconcile with a meteoric origin of the water from which the secondary minerals at Yucca Mountain precipitated; instead they point to the deep-seated provenance of the mineral-forming waters and their introduction into the unsaturated zone from below, i.e. a hypogene origin.     

Diagenesis of English Lower Jurassic limestones as inferred from oxygen and carbon isotope analysis

Fifty-seven samples of mostly Liassic limestones and calcite spar were subjected to mass spectrometer analysis to determine δ¹³C and δ¹⁸O. The results are used to compare and interpret the changing isotopic composition through time of calcite-precipitating pore fluids and to assess the influence of rate and type of sedimentation, diagenetic reactions and meteoric water influx. In general microsparite beds and concretions formed sooner after deposition in Dorset than in Yorkshire, where sedimentation rates were usually higher. Calcite horizons in the Bridport Sands Formation of Dorset are entirely diagenetic in origin. Carbon isotope data from concretions in the Jet Rock Formation of Yorkshire support a model of changing organic reactions with increasing depth of burial. The influence of meteoric waters is substantially restricted to the formation of post-Liassic veins.     

History of anthropogenic nitrogen input to the German Bight/SE North Sea as reflected by nitrogen isotopes in surface sediments,sediment cores and hindcast models

The German Bight/SE North Sea is considered a hot-spot of river-induced eutrophication, but the scarce observational data of river nitrate loads prior to the 1970s complicate the assessment of target conditions for environmental management and legislation. Stable nitrogen isotope ratios (δ¹⁵N) in sediment records can be used to decipher historical river nitrate contributions. To better constrain pre-1970s conditions, we determined δ¹⁵N in archive sediment samples (1950–1969) and dated cores from the Helgoland depositional area. We also modeled the δ¹⁵N in past situations (1960 and 1860) using an N-isotope-tracking ecosystem model. The modeled spatial distribution of δ¹⁵N in sediments for 1960 conditions and the observed spatial pattern of δ¹⁵N in archive sediment samples (1950–1969) represent a period of moderate eutrophication. The modeled spatial distribution of δ¹⁵N in sediments for 1860 conditions (pre-industrial) showed a moderate δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N<4‰) to the open sea (δ¹⁵N∼5‰). This pattern contrasts with the δ¹⁵N pattern in modern surface sediments, which exhibits a steep and inverted δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N>9‰) to the open sea (δ¹⁵N<7‰). Modeled δ¹⁵N for 1860 conditions are consistent with δ¹⁵N values observed in dated sediment cores that span the last 900 years. Value of δ¹⁵N in sediment cores increased from approximately 1860 to 2000 by 2.5‰. The increasing trend reflects changes in the abundance and isotopic composition of riverine nitrate loads caused by anthropogenic activities. Sensitivity tests suggest that loads and isotopic ratios of nitrogen forms other than nitrate (ammonium and organic nitrogen) have minor impact on the modeled surface sediments, despite their higher abundance in the riverborne loads in the past. Our results suggest that eutrophication of the German Bight predates the 1960 period of documented rapidly increasing river loads. Pre-industrial levels of δ¹⁵N modeled with 28% of the modern annual (1990–1999) atmospheric loads and 10% of the modern annual river loads agree best with levels of δ¹⁵N (∼6‰) observed in sediments of the cores dated to 1860.     

The sulfur isotopic composition of Neoproterozoic seawater sulfate: implications for a snowball Earth?

The present study employs a method for analysis of the sulfur isotopic composition of trace sulfate extracted from carbonates collected in Namibia in order to document secular variations in the sulfur isotopic composition of Neoproterozoic oceanic sulfate and to assess variations in the sulfur cycle that may have accompanied profound climatic events that have been described as the snowball Earth hypothesis. The carbonates in the Otavi Group of Northwest Namibia contain 3-295 ppm sulfate. Positive excursions, to a high of 40‰ (CDT), occur above the lower (Chuos Formation) and upper (Ghaub Formation) glacial intervals in the Rasthof and Maieberg cap carbonates, respectively. Positive excursions at the top of the Rasthof Formation (reaching 51‰) and within the overlying Gruis Formation (34‰) do not appear to correspond to glaciation. The δ³⁴S_sulfate values within the Ombaatjie Formation exhibit shifts over relatively short stratigraphic intervals (tens of meters), varying between ∼15 and 25‰. Cap carbonates from Australia exhibit positive δ³⁴S_pyrite trends with amplitudes similar to those of Namibian δ³⁴S_sulfate, although, more data are necessary to firmly establish these δ³⁴S trends as global in nature. δ³⁴S_sulfate excursions found in Namibian cap carbonates are consistent with the snowball Earth hypothesis in that they appear to reflect nearly complete reduction of sulfate in an isolated, anoxic global ocean, although, there are other mechanisms that may have facilitated these large shifts in δ³⁴S_sulfate. Regardless, the low sulfate concentrations in Otavi carbonates, the high amplitude variability of the δ³⁴S_sulfate curve, and the apparently full reduction of sulfate (as implied from δ³⁴S_pyrite data), even in strata low in C_org, suggest that Neoproterozoic oceanic sulfate concentrations were much lower than modern values. Additionally, the buildup of ferrous iron and banded-iron formations during the Sturtian glacial event would indicate that Fe supply exceeded sulfide availability during the glacials and/or that all sulfide was fixed and buried. This could be construed as further evidence in support of low oceanic sulfate (and sulfide) at this time.     

Water isotopic variability in Mallorca: a path to understanding past changes in hydroclimate

This paper reports the first results on δ¹⁸O and δ²H analysis of precipitations, cave drip waters, and groundwaters from sites in Mallorca (Balearic Islands, western Mediterranean), a key region for paleoclimate studies. Understanding the isotopic variability and the sources of moisture in modern climate systems is required to develop speleothem isotope‐based climate reconstructions. The stable isotopic composition of precipitation was analysed in samples collected between March 2012 and March 2013. The values are in the range reported by GNIP Palma station. Based on these results, the local meteoric water line (LMWL) δ²H = 7.9 (±0.3) δ¹⁸O + 10.8 (±2.5) was derived, with slightly lower slope than Global Meteoric Water Line. The results help tracking two main sources of air masses affecting the study sites: rain events with the highest δ¹⁸O values (> ?5‰) originate over the Mediterranean Sea, whereas the more depleted samples (< ?8‰) are sourced in the North Atlantic region. The back trajectory analysis and deuterium excess values, ranging from 0.4 to 18.4‰, further support our findings. To assess the isotopic variation across the island, water samples from eight caves were collected. The δ¹⁸O values range between ?6.9 and ?1.6‰. With one exception (Artà), the isotopic composition of waters in caves located along the coast (Drac, Vallgornera, Cala Varques, Tancada, and Son Sant Martí) indicates Mediterranean‐sourced moisture masses. By contrast, the drip water δ¹⁸O values for inland caves (Campanet, ses Rates Pinyades) or developed under a thick (>50 m) limestone cap (Artà) exhibit more negative values. A well‐homogenized aquifer supplied by rainwaters of both origins is clearly indicated by groundwater δ¹⁸O values, which show to be within 2.4‰ of the unweighted arithmetic mean of ?7.4‰. Although limited, the isotopic data presented here constitute the baseline for future studies using speleothem δ¹⁸O records for western Mediterranean paleoclimate reconstructions. Copyright © 2016 John Wiley & Sons, Ltd.     

Nitrogen cycling in the German Bight (SE North Sea) — Clues from modelling stable nitrogen isotopes

Nitrogen isotope values (δ¹⁵N) of surface sediments in the German Bight of the North Sea exhibit a significant gradient from values of 5–6‰ of the open shelf sea to values above 11‰ in the German Bight. This signal has been attributed to high reactive N (N_r) loading enriched in ¹⁵N from rivers and the atmosphere. To better understand the processes that determine the intensity and spatial distribution of δ¹⁵N anomalies in surface sediments, and to explore their usefulness for reconstructions of pristine N-input from rivers, we modeled the cycling of the stable isotopes ¹⁴N and ¹⁵N in reactive nitrogen through the ecosystem of the central and southern North Sea (50.9–57.3°N, 3.4°W−9.2°E) for the year 1995. The 3D-ecosystem model ECOHAM amended with an isotope-tracking module was validated by δ¹⁵N data of surface sediments within the model domain. A typical marine value (δ¹⁵N_nitrate=5‰) was prescribed for nitrate advected into the model domain at the seaside boundaries, whereas δ¹⁵N_nitrate of river inputs were those measured bi-monthly over 1 year; δ¹⁵N values of atmospheric deposition were set to 6‰ and 7‰ for NO_x and NH_y, respectively. The simulated δ¹⁵N values of different nitrogen compounds in the German Bight strongly depend on the mass transfers in the ecosystem. These fluxes, summarized in a nitrogen budget for 1995, give an estimate of the impacts of hydrodynamical and hydrological boundary conditions, and internal biogeochemical transformations on the nitrogen budget of the bight.     

Systematic change of foraminiferal Mg/Ca ratios across a strong salinity gradient

The Mg/Ca ratio of foraminiferal calcite is an important proxy for estimating past ocean temperatures. Used in conjunction with δ¹⁸O of foraminiferal calcite it allows deconvolution of temperature and ice-volume signals to infer past ocean temperatures and salinities (assuming the relationship between seawater δ¹⁸O and salinity is known). Such work assumes that temperature is the only, or at least the dominant, environmental controller of foraminiferal Mg/Ca. The semi-enclosed Mediterranean Sea, where salinity varies from 36 to 40 psu over a seasonal temperature range of between only 5 °C to 8 °C, provides a relevant setting to test this assumption outside the laboratory. In this study, planktonic foraminifera (O. universa, G. siphonifera, G. bulloides and G. ruber (white) and (pink)) were picked from 11 box core tops spanning the Mediterranean salinity gradient and analysed for their trace-element concentrations. Mg/Ca ratios are higher, for the associated calcification temperatures, than in other regions where calibrations have been conducted and correlate poorly with calcification temperature. Mg/Ca ratios are particularly high for samples from the Eastern Mediterranean where salinity is unusually high. Correlations of Mg/Ca with the calcification salinity are statistically significant with Mg/Ca changing by 15–59% per psu, suggesting that salinity may act as a control on Mg/Ca ratios in addition to the dominant temperature control. We show that contamination by non-carbonate material and diagenetic high-Mg carbonate overgrowths cannot account for the observed trend of increasing Mg/Ca with salinity. A relationship between Mg/Ca and salinity is also suggested by re-analysis of calibrations from open-ocean settings. These new Mediterranean results are from a region with unusually high salinity but suggest that the effects of salinity on the Mg/Ca palaeothermometer should be considered even in open-ocean settings, particularly where large salinity changes occurred in the past.     

Authigenic carbonates in sediments from the Gulf of Mexico

The carbon isotopic composition of diagenetic dolomite and calcite in some sediments of the Gulf of Mexico varies between “normal-marine” (δ¹³C ca. 0‰) and −14.6‰ which suggests that biogenic CO₂ contributed to the carbonate formation. The δ¹³O values of dolomite and coexisting calcite are very similar but variable down-core.Dolomite and calcite precipitated early from pore water where SO₄²⁻ was not reduced. However, during (and after?) SO₄²⁻ reduction dolomite and calcite still formed and there are at least two generations of carbonate minerals present.     

Space weathering processes on airless bodies: Fe isotope fractionation in the lunar regolith

Nanophase Fe metal grains (np-Fe°) are a product of space weathering, formed by processes related to meteorite impacts, and solar-wind sputtering on airless planetary bodies, such as the Moon. Iron isotopes of lunar soils are fractionated during these processes, and the np-Fe° in the finest (<10 μm), mature, size fractions of the soil become enriched in heavier isotopes by ∼0.3‰ in ⁵⁶Fe/⁵⁴Fe in comparison to the bulk rocks (0.03±0.05‰), from which the soil was formed. A positive correlation of δ⁵⁶Fe values with the soil maturity index, I_S/FeO, suggests that the high δ⁵⁶Fe values reflect production of nanophase Fe metal that is produced by space weathering that occurs on airless planetary bodies. Furthermore, the enrichment of δ⁵⁶Fe in the smallest size fraction of lunar soils supports a model for creation of np-Fe° through vapor deposition induced by micrometeorites, as well as that by solar-wind sputtering.     

Massive barite deposits and carbonate mineralization in the Derugin Basin, Sea of Okhotsk: precipitation processes at cold seep sites

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (∼1%) in the barite fabric imply the presence of H₂S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative δ¹³C values of these carbonates (>−43.5‰ PDB) indicate methane as major carbon source; δ¹⁸O values between 4.04 and 5.88‰ PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with ¹⁴C-ages ranging from 20?680 to >49?080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO₄^2- concentrations and a parallel increase of H₂S with depth. Additionally, S and O isotope data of barite sulfate (δ³⁴S: 21.0-38.6‰ CDT; δ¹⁸O: 9.0-17.6‰ SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with ‘normal’ seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49?000 yr.     

The oxygen isotopic composition and temperature of Southern Ocean bottom waters during the last glacial maximum

We provide two new determinations of the oxygen isotopic composition of seawater during the last glacial maximum (LGM). High-resolution oxygen isotopic measurements were made on interstitial waters from Ocean Drilling Program (ODP) Sites 1168 and 1170 in the southeast Indian Ocean sector of the Southern Ocean. We use a diffusion-advection numerical model to calculate the glacial-interglacial change in bottom-water δ¹⁸O_sw from the pore water δ¹⁸O profiles; the first such determinations from this part of the oceans. Statistical analyses of the model runs indicate that Circumpolar Deep Water (CDW) δ¹⁸O_sw changed by 1.0-1.1±0.15‰ since the last glacial maximum (LGM). Our results are consistent with a previous calculation from a South Atlantic Southern Ocean location (ODP Site 1093) also situated within CDW. The new values determined in this study, together with previous estimates, are converging on a global average Δδ¹⁸O_sw of 1.0-1.1‰.Using the calculated bottom-water δ¹⁸O_sw, we have extracted the temperature component from the benthic foraminiferal δ¹⁸O record at Sites 1168 and 1170. Since the LGM, bottom waters at these two sites warmed by 2.6 and 1.9°C, respectively. The absolute temperature estimates for the LGM (−0.5°C [Θ=−0.6°C] at Site 1168 and −0.2°C [Θ=−0.4°C] at Site 1170) are slightly warmer than those reported from previous studies using the same technique, but are consistent with more homogenous deep-ocean temperatures during the LGM relative to the modern.     

Isotope distribution of dissolved carbonate species in southeastern coastal aquifers of Sicily (Italy)

Concentrations of major ions and the δ¹³C composition of dissolved inorganic carbon in groundwater and submarine groundwater discharges in the area between Siracusa and Ragusa provinces, southeastern Sicily, representing coastal carbonate aquifers, are presented and discussed. Most of groundwater analysed belongs to calcium bicarbonate type, in agreement with the geological nature of carbonate host rocks. Carbonate groundwater acquires, besides the dissolution of carbonate minerals, dissolved carbon (and the relative isotopic composition) from the atmosphere and from soil biological activity. In fact, δ¹³C values and total dissolved inorganic carbon contents show that both these sources contribute to carbon dissolved species in the waters studied. Finally, mixing with seawater in the second main factor of groundwater mineralization Copyright © 2007 John Wiley & Sons, Ltd.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Later Pleistocene/Holocene climate conditions of Qinghai-Xizhang Plateau (Tibet) based on carbon and oxygen stable isotopes of Zabuye Lake sediments

We present a time series of carbon and oxygen stable isotope records of the last 30?000 ¹⁴C years throughout the last glacial-postglacial cycle from western Qinghai-Xizhang (Tibet) Plateau. A 20-m core drilled in the south basin of Zabuye Salt Lake was analyzed for inorganic and organic carbon and total sulfur contents, δ¹³C and δ¹⁸O values of carbonates. Our results indicate that climatic changes have led to a drastic negative shift of stable isotope ratios at the transition between the Last Full Glacial and the postglacial phase during Later Pleistocene times (∼16.2 kyr BP), and a rapid positive shift at the transition from Pleistocene to Holocene (∼10.6 kyr BP). The first shift is marked by the drop of δ¹⁸O_carb values of about 10‰ (from +2 to −8‰) and δ¹³C_carb values of about 3‰ (from 5 to 2‰). The second shift which occurred at the transition from Pleistocene to Holocene was of similar magnitude but in the opposite direction. Isotope data, combined with total organic and inorganic carbon contents and the lithological composition of the core, suggest this lake was an alluvial pre-lake environment prior to ca. 28 ¹⁴C kyr BP. During ca. 28-16.2 ¹⁴C kyr BP, Zabuye Lake was likely a moderately deep lake with limited outflow. The cool and arid glacial climate led the lake level to drop drastically. Extended residence time overwhelmed the lower temperature and caused a steady increase of δ¹³C_carb and δ¹⁸O_carb values and total inorganic carbon content in the sediments. During ca. 16.2-10.6 ¹⁴C kyr BP, this lake probably overflowed and received abundant recharge from melting glaciers when the deglaciation was in its full speed. A spike of markedly enhanced δ¹³C_carb and δ¹⁸O_carb is seen at ∼11.5 kyr BP, probably due to the isotopic effects left behind by the short but severe Younger Dryas (YD) event. After ca. 10.6 ¹⁴C kyr BP, Zabuye Lake probably closed its surface outflow, due to strong desiccation and drastic climate warming. The Early and Middle Holocene were characterized by unstable climatic conditions with alternating warmer/cooler episodes as indicated by the severe fluctuations of total organic carbon, δ¹³C and δ¹⁸O values. A hypersaline salt lake environment was finally formed at Zabuye after ∼5 ¹⁴C kyr BP when the mirabilite and halite concentrations steadily increased and became the dominant minerals in the sediments. Severe imbalance of inflow/outflow resulted in the drastic increase of total sulfur, δ¹³C_carb and δ¹⁸O_carb values and dominance of halite in the lake since ca. 3.8 kyr BP to present.     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.