Investigation of young water inflow in karst aquifers using SF6–CFC–3H/He–85Kr–39Ar and stable isotope components

Karst aquifers are known for their wide distribution of water transfer velocities. From this observation, a multiple geochemical tracer approach seems to be particularly well suited to provide a significant assessment of groundwater flows, but the choice of adapted tracers is essential. In this study, several common tracers in karst aquifers such as physicochemical parameters, major ions, stable isotopes, and d13C to more specific tracers such as dating tracers – 14C, 3H, 3H–3He, CFC-12, SF6 and 85Kr, and 39Ar – were used, in a fractured karstic carbonated aquifer located in Burgundy (France). The information carried by each tracer and the best sampling strategy are compared on the basis of geochemical monitoring done during several recharge events and over longer time periods (months to years). This study’s results demonstrate that at the seasonal and recharge event time scale, the variability of concentrations is low for most tracers due to the broad spectrum of groundwater mixings. The tracers used traditionally for the study of karst aquifers, i.e., physicochemical parameters and major ions, efficiently describe hydrological processes such as the direct and differed recharge, but require being monitored at short time steps during recharge events to be maximized. From stable isotopes, tritium, and Cl� contents, the proportion of the fast direct recharge by the largest porosity was estimated using a binary mixing model. The use of tracers such as CFC-12, SF6, and 85Kr in karst aquifers provides additional information, notably an estimation of apparent age, but they require good preliminary knowledge of the karst system to interpret the results suitably. The CFC-12 and SF6 methods efficiently determine the apparent age of baseflow, but it is preferable to sample the groundwater during the recharge event. Furthermore, these methods are based on different assumptions such as regional enrichment in atmospheric SF6, excess air, and flow models among others. 85Kr and 39Ar concentrations can potentially provide a more direct estimation of groundwater residence time. Conversely, the 3H–3He method is inefficient in the karst aquifer for dating due to 3He degassing.

Evidence for extinct Cs-135 from Ba isotopes in Allende CAIs?

he abundance and distribution of isotopes throughout the Solar System can be used to constrain the number and type of nucleosynthetic events that contributed material to the early nebula. Barium is particularly well suited to quantifying the degree of isotope heterogeneity in the Solar System because it comprises seven stable isotopes that were synthesized by three different nucleosynthetic processes (s-, r-, and p-processes), all of which contributed material to the Solar System. There is also potential contribution to 135Ba from short-lived radioisotope 135Cs, conclusive evidence for which is yet to be reported. Four Allende (CV3) Ca,Al-rich inclusions (CAI 1, CAI 2, CAI 4, CAI 5) and one Allende dark inclusion (DI) were analyzed for Ba isotope variability. Two CAIs (CAI 2 and CAI 5) display 135Ba excesses that are not accompanied by 137Ba anomalies. Calcium–aluminum-rich inclusion 1 displays a 135Ba excess that is possibly coupled with a 137Ba excess, and the remaining refractory inclusions (CAI 2 and DI) have terrestrial Ba isotope compositions. These Ba isotope data are presented in conjunction with published whole rock Ba isotope data from individual Allende CAIs. The enrichment in 135Ba and absence of coupled 137Ba excesses in CAI 2 and CAI 5 is interpreted to indicate that the anomalies are not purely nucleosynthetic in origin but also contain contributions (16–48 ppm) from the decay of short-lived 135Cs. The majority of Allende CAIs studied to date may also have similar contributions from 135Cs on the basis of higher than expected 135Ba excesses if the Ba isotope anomalies were purely nucleosynthetic in origin. The 135Ba anomalies appear not to be coupled with superchondritic Cs/Ba, which may imply that the contribution to 135Ba did not occur via in situ decay of live 135Cs. However, it is feasible that the CAIs had a superchondritic Cs/Ba during decay of 135Cs, but Cs was subsequently removed from the system during aqueous alteration on the parent body. An alternative scenario is the potential existence of a transient high-temperature reservoir having superchondritic Cs/Ba in the early Solar System while 135Cs was extant, which enabled a radiogenic 135Ba signature to develop in some early condensates. The nucleosynthetic source of 135Cs can be determined by reconciling the predicted astrophysical 135Cs abundance with its measured abundance in meteorites. Further, the currently accepted initial 135Cs/133Cs of the Solar System, [135Cs/133Cs]0, may be underestimated because the spread of Cs/Ba among samples is small and the range of excess 135Ba is limited thus leading to inaccuracies when estimating [135Cs/133Cs]0. If the initial meteoritic abundance of 135Cs was indeed higher than is currently thought, the most probable stellar source of short-lived radioisotopes was a nearby core-collapse supernova and/or the Wolf–Rayet wind driven by its progenitor.

Growth rates and stable carbon and oxygen isotope record of corals from the Red Sea

Monthly delta18O records of 2 coral colonies (Porites cf. lutea and P. cf. nodifera) from different localities (Aqaba and Eilat) from the northern Gulf of Aqaba, Red Sea, were calibrated with recorded sea surface temperatures (SST) between 1988 and 2000. The results show high correlation coefficients between SST and delta18O. Seasonal variations of coral delta18O in both locations could explain 91% of the recorded SST. Different delta18O/SST relations from both colonies and from the same colonies were obtained, indicating that delta18O from coral skeletons were subject to an extension rate effect. Significant delta18O depletions are associated with high extension rates and higher values with low extension rates. The relation between coral skeletal delta18O and extension rate is not linear and can be described by a simple exponential model. An inverse relationship extends over extension rates from 1 to 5 mm/yr, while for more rapidly growing corals and portions of colonies the relation is constant and the extension rate does not appear to have a significant effect. We recommend that delta18O values be obtained from fast-growing corals or from portions in which the isotopic disequilibrium is fairly constant (extension rate >5 mm/yr). The results show that interspecific differences in corals may produce a significant delta18O profile offset between 2 colonies that is independent of environmental and extension-rate effects. We conclude that the rate of skeletal extension and the species of coral involved have an important influence on coral delta18O and must be considered when using delta18O records for paleoclimatic reconstructions.

Water stable oxygen isotope records from six Antarctic ice core sites for the present and last interglacial periods

We compare the present and last interglacial periods as recorded in Antarctic water stable isotope records now available at various temporal resolutions from six East Antarctic ice cores: Vostok, Taylor Dome, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML), Dome Fuji and the recent TALDICE ice core from Talos Dome. We first review the different modern site characteristics in terms of ice flow, meteorological conditions, precipitation intermittency and moisture origin, as depicted by meteorological data, atmospheric reanalyses and Lagrangian moisture source diagnostics. These different factors can indeed alter the relationships between temperature and water stable isotopes. Using five records with sufficient resolution on the EDC3 age scale, common features are quantified through principal component analyses. Consistent with instrumental records and atmospheric model results, the ice core data depict rather coherent and homogenous patterns in East Antarctica during the last two interglacials. Across the East Antarctic plateau, regional differences, with respect to the common East Antarctic signal, appear to have similar patterns during the current and last interglacials. We identify two abrupt shifts in isotopic records during the glacial inception at TALDICE and EDML, likely caused by regional sea ice expansion. These regional differences are discussed in terms of moisture origin and in terms of past changes in local elevation histories, which are compared to ice sheet model results. Our results suggest that elevation changes may contribute significantly to inter-site differences. These elevation changes may be underestimated by current ice sheet models

Planktonic and benthic stables Isotopes, age model and carbon analysis of HUD91/039 from the northernmost Baffin Bay

A multiproxy study of palaeoceanographic and climatic changes in northernmost Baffin Bay shows that major environmental changes have occurred since the deglaciation of the area at about 12 500 cal. yr BP. The interpretation is based on sedimentology, benthic and planktonic foraminifera and their isotopic composition, as well as diatom assemblages in the sedimentary records at two core sites, one located in the deeper central part of northernmost Baffin Bay and one in a separate trough closer to the Greenland coast. A revised chronology for the two records is established on the basis of 15 previously published AMS 14C age determinations. A basal diamicton is overlain by laminated, fossil-free sediments. Our data from the early part of the fossiliferous record (12 300 - 11 300 cal. yr BP), which is also initially laminated, indicate extensive seasonal sea-ice cover and brine release. There is indication of a cooling event between 11 300 and 10 900 cal. yr BP, and maximum Atlantic Water influence occurred between 10 900 and 8200 cal. yr BP (no sediment recovery between 8200 and 7300 cal. yr BP). A gradual, but fluctuating, increase in sea-ice cover is seen after 7300 cal. yr BP. Sea-ice diatoms were particularly abundant in the central part of northernmost Baffin Bay, presumably due to the inflow of Polar waters from the Arctic Ocean, and less sea ice occurred at the near-coastal site, which was under continuous influence of the West Greenland Current. Our data from the deep, central part show a fluctuating degree of upwelling after c. 7300 cal. yr BP, culminating between 4000 and 3050 cal. yr BP. There was a gradual increase in the influence of cold bottom waters from the Arctic Ocean after about 3050 cal. yr BP, when agglutinated foraminifera became abundant. A superimposed short-term change in the sea-surface proxies is correlated with the Little Ice Age cooling.

Stable isotope ratios from foraminfera in Kara Sea sediments

Ostracods secrete their valve calcite within a few hours or days, therefore, its isotopic composition records ambient environmental conditions of only a short time span. Hydrographic changes between the calcification of individuals lead to a corresponding range (max.-min.) in the isotope values when measuring several (>=5) single valves from a specific sediment sample. Analyses of living (stained) ostracods from the Kara Sea sediment surface revealed high ranges of >2per mil of d18O and d13C at low absolute levels (d18O: <3per mil, d13C: <-3per mil) near the river estuaries of Ob and Yenisei and low ranges of not, vert, similar1per mil at higher absolute levels (d18O: 2-5.4per mil, d13C: -3 per mil to -1.5per mil) on the shelf and in submarine paleo-river channels. Comparison with a hydrographic data base and isotope measurements of bottom water samples shows that the average and the span of the ostracod-based isotope ranges closely mirror the long-term means and variabilities (standard deviation) of bottom water temperature and salinity. The bottom hydrography in the southern part of the Kara Sea shows strong response to the river discharge and its extreme seasonal and interannual variability. Less variable hydrographic conditions are indicative for deeper shelf areas to the north, but also for areas near the river estuaries along submarine paleo-river channels, which act as corridors for southward flowing cold and saline bottom water. Isotope analyses on up to five single ostracod valves per sample in the lower section (8-7 cal. ka BP) of a sediment core north of Yenisei estuary revealed d18O and d13C values which on average are lower by 0.6? in both, d18O and d13C, than in the upper core section (<5 cal. ka BP). The isotope shifts illustrate the decreasing influence of isotopically light river water at the bottom as a result of the southward retreat of the Yenisei river mouth from the coring site due to global sea level rise. However, the ranges (max.-min.) in the single-valve d18O and d13C data of the individual core samples are similar in the upper and in the lower core section, although a higher hydrographic variability is expected prior to 7 cal. ka BP due to river proximity. This lack of variability indicates the southward flow of cold, saline water along a submarine paleo-river channel, formerly existing at the core location. Despite shallowing of the site due to sediment filling of the channel and isostatic uplift of the area, the hydrographic variability at the core location remained low during the Late Holocene, because the shallowing proceeded synchronously with the retreat of the river mouth due to the global sea level rise

Stable-isotope records from Dronning Maud Land, Antarctica

The European Project for Ice Coring in Antarctica (EPICA) includes a comprehensive pre-site survey on the inland ice plateau of Dronning Maud Land. This paper focuses on the investigation of the 18O content of shallow firn and ice cores. These cores were dated by profiles derived from dielectric-profiling and continuous flow analysis measurements. The individual records were stacked in order to obtain composite chronologies of 18O contents and accumulation rates with enhanced signal-to-noise variance ratios.These chronologies document variations in the last 200 and 1000 years.The 18O contents and accumulation rates decreased in the 19th century and increased during the 20th century.Using the empirical relationships between stable isotopes, accumulation rates and the 10m firn temperature, the variation of both parameters can be explained by the same temperature history.But other causes for these variations, such as the build-up of the snow cover, cannot be excluded. A marked feature of the 1000 year chronology occurs during the period AD 1180-1530 when the 18O contents remains below the long-term mean. Cross-correlation analyses between five cores from the Weddell Sea region and Dronning Maud Land show that 18O records can in some periods be positively correlated and in others negatively correlated, indicating a complex climatic history in time and space.

Stable carbon and oxygen isotope composition of Late Cretaceous benthic foraminifera from the southern South Atlantic

The stable carbon and oxygen isotope composition of different benthic foraminiferal species of the latest Campanian and earliest Maastrichtian from Ocean Drilling Project Hole 690C (Weddell Sea, southern South Atlantic, ~1800 m paleowater depth) have been investigated. The total range of measured isotope values of all samples exceeds ~4 per mil for delta 13C and 1.1 per mil for delta 18O. Carbon isotope values of proposed deep infaunal species are generally similar or only slightly lower when compared to proposed epifaunal to shallow infaunal species. Interspecific differences vary between samples probably reflecting temporal changes in organic carbon fluxes to the sea floor. Constantly lower delta 13C values for Pullenia marssoni and Pullenia reussi suggest the deepest habitat for these species. The strong depletion of delta 13C values by up to 3 per mil within lenticulinids may be attributed to a deep infaunal microhabitat, strong vital effects, or different feeding strategy when compared to other species or modern lenticulinids. The mean delta 18O values reveal a strong separation of epifaunal to shallow infaunal and deep infaunal species. Epifaunal to shallow infaunal species are characterized by low delta 18O values, deep infaunal species by higher values. This result possibly reflects lower metabolic rates and longer life cycles of deep infaunal species or the operating of a pore water [CO3]2- effect on the benthic foraminiferal stable isotopes. Pyramidina szajnochae shows an enrichment of oxygen isotopes with test size comprising a total of 0.6 per mil between 250 and 1250 µm shell size. Although delta 13C lacks a corresponding trend these data likely represent the presence of changes in metabolic rates during ontogenesis. These results demonstrate the general applicability of multi-species stable isotope measurements of pristine Cretaceous benthic foraminifera to reconstruct past microhabitats and to evaluate biological and environmental effects on the stable isotope composition.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

(Table 1) Stable carbon and nitrogen isotopic ratios of potential prey species of bearded seals (Erignathus barbatus), Svalbard

Changing patterns of sea-ice distribution and extent have measurable effects on polar marine systems. Beyond the obvious impacts of key-habitat loss, it is unclear how such changes will influence ice-associated marine mammals in part because of the logistical difficulties of studying foraging behaviour or other aspects of the ecology of large, mobile animals at sea during the polar winter. This study investigated the diet of pregnant bearded seals (Erignathus barbatus) during three spring breeding periods (2005, 2006 and 2007) with markedly contrasting ice conditions in Svalbard using stable isotopes (d13C and d15N) measured in whiskers collected from their newborn pups. The d15N values in the whiskers of individual seals ranged from 11.95 to 17.45 per mil, spanning almost 2 full trophic levels. Some seals were clearly dietary specialists, despite the species being characterised overall as a generalist predator. This may buffer bearded seal populations from the changes in prey distributions lower in the marine food web which seems to accompany continued changes in temperature and ice cover. Comparisons with isotopic signatures of known prey, suggested that benthic gastropods and decapods were the most common prey. Bayesian isotopic mixing models indicated that diet varied considerably among years. In the year with most fast-ice (2005), the seals had the greatest proportion of pelagic fish and lowest benthic invertebrate content, and during the year with the least ice (2006), the seals ate more benthic invertebrates and less pelagic fish. This suggests that the seals fed further offshore in years with greater ice cover, but moved in to the fjords when ice-cover was minimal, giving them access to different types of prey. Long-term trends of sea ice decline, earlier ice melt, and increased water temperatures in the Arctic are likely to have ecosystem-wide effects, including impacts on the forage bases of pagophilic seals.

Planktonic foraminifera and their stable isotope record of MICNESS samples off Cape Cod

Monthly samples of stratified plankton tows taken from the slope waters off Cape Cod nearly 25 years ago are used to describe the seasonal succession of planktonic foraminifera and their oxygen isotope ratios. The 15°C seasonal cycle of sea surface temperature (SST) accounts for a diverse mixture of tropical to subpolar species. Summer samples include various Globigerinoides and Neogloboquadrina dutertrei, whereas winter and early spring species include Globigerina bulloides and Neogloboquadrina pachyderma (dextral). Globorotalia inflata lives all year but at varying water depths. Compared with the fauna in 1960-1961 (described by R. Cifelli), our samples seem warmer. Because sea surface salinity varies little during the year, d18O is mostly a function of SST. Throughout the year, there are always species present with d18O close to the calculated isotopic equilibrium of carbonate with surface seawater. This raises the possibility that seasonality can be estimated directly from the range of d18O in a sediment sample provided that the d18O-salinity relationship is the same as today.

Middle to late Miocene stable isotope record of benthic foraminifera from ODP Site 184-1146

We present high-resolution (2-3 kyr) benthic foraminiferal stable isotopes in a continuous, well-preserved sedimentary archive from the West Pacific Ocean (Ocean Drilling Program Site 1146), which track climate evolution in unprecedented resolution over the period 12.9 to 8.4 Ma. We developed an astronomically tuned chronology over this interval and integrated our new records with published isotope data from the same location to reconstruct long-term climate and ocean circulation development between 16.4 and 8.4 Ma. This extended perspective reveals that the long eccentricity (400 kyr) cycle is prominently encoded in the d13C signal over most of the record, reflecting long-term fluctuations in the carbon cycle. The d18O signal closely follows variations in short eccentricity (100 kyr) and obliquity (41 kyr). In particular, the obliquity cycle is prominent from ~14.6 to 14.1 Ma and from ~9.8 to 9.2 Ma, when high-amplitude variability in obliquity is congruent with low-amplitude variability in short eccentricity. The d18O curve is additionally characterized by a series of incremental steps at ~14.6, 13.9, 13.1, 10.6, 9.9, and 9.0 Ma, which we attribute to progressive deep water cooling and/or glaciation episodes following the end of the Miocene climatic optimum. On the basis of d18O amplitudes, we find that climate variability decreased substantially after ~13 Ma, except for a remarkable warming episode at ~10.8-10.7 Ma at peak insolation during eccentricity maxima (100 and 400 kyr). This transient warming, associated with a massive negative carbon isotope shift, is reminiscent of intense global warming events at eccentricity maxima during the Miocene climatic optimum.

Age model and stable isotope record of eastern equatorial Pacific sediment cores

Six deep sea cores from the eastern equatorial Pacific (EEP) were analyzed for planktonic foraminifera and stable isotopes in order to reconstruct sea surface temperatures (SST) for the last 40 ka. South of the Equatorial Front the abundance of Globorotalia inflata increased, and SST decreased by >5°C (core ODP846B), creating a stronger SST meridional gradient and advection of the Peru Current than present for the ~16-35 ka interval. A sharper SST meridional gradient forced stronger Choco jet events and a moisture increase in western Colombia, which supplied, through the San Juan River and the south-flowing equatorial and the Peru-Chile countercurrents, abundant hemipelagic quartz over the northern Peru basin (core TR163-31B). The Choco jet, and its associated mesoscale convective cells, provoked an increase in snow precipitation over the Central Cordillera of Colombia and the advance of the Murillo glacier. In synchrony with the intensified Choco jet events, the "dry island" effect over the Eastern Cordillera of Colombia intensified, and the level of Fuquene Lake dropped.