Gas discharges for continental Spain: geochemical and isotopic features

In this work the results of a geochemical and isotopic survey of 37 gas discharges was carried out in continental Spain are presented and discussed. On the basis of the gas chemical composition, four different areas can be distinguished, as follows: 1) Selva-Emborda (SE) region; 2) Guadalentin Valley (GV); 3) Campo de Calatrava (CC) and 3) the inner part of Spain (IS). The SE, GV and CC areas are characterized by CO2-rich gases, while IS has N2 as main gas compound. The CO2-rich gases can be distinguished at their turn on the basis on the helium and carbon isotopic composition. The SE and CC areas have a strong mantle signature (up to 3 Ra). Nevertheless, the carbon isotopic composition of CC is within the mantle range and that of SE is slightly more negative (down to -8‰ PDB). The GV gases have a lower mantle signature (61 Ra) with respect to SE and CC and more negative carbon isotopes (6-10‰ PDB). It is worth to mention that the SE, GV and CC areas are related to the youngest volcanic activity in continental Spain, for example the Garrotxa Volcanic Field in Catalonia records the latest event dated at 10,000 years, and the isotopic features, particularly those of helium, are suggesting the presence of magmatic bodies still cooling at depth. The N2-rich gases, i.e. those from the IS area, has an atmospheric origin, as highlighted by the N2/Ar ratio that ranges between those of air and ASW (Air Saturated Water). The isotopic composition of carbon is distinctly negative (down to -21‰ PDB) and that of helium is typically crustal (0.02-0.08 Ra), confirming that these gas discharges are related to a relatively shallow source.

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ≈70‰) shifts in δ13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70‰) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Characteristics of the deep ocean carbon system during the past 150,000 years: ΣCO2 distributions, deep water flow patterns, and abrupt climate change

Studies of carbon isotopes and cadmium in bottom-dwelling foraminifera from ocean sediment cores have advanced our knowledge of ocean chemical distributions during the late Pleistocene. Last Glacial Maximum data are consistent with a persistent high-ΣCO2 state for eastern Pacific deep water. Both tracers indicate that the mid-depth North and tropical Atlantic Ocean almost always has lower ΣCO2 levels than those in the Pacific. Upper waters of the Last Glacial Maximum Atlantic are more ΣCO2-depleted and deep waters are ΣCO2-enriched compared with the waters of the present. In the northern Indian Ocean, δ13C and Cd data are consistent with upper water ΣCO2 depletion relative to the present. There is no evident proximate source of this ΣCO2-depleted water, so I suggest that ΣCO2-depleted North Atlantic intermediate/deep water turns northward around the southern tip of Africa and moves toward the equator as a western boundary current. At long periods (>15,000 years), Milankovitch cycle variability is evident in paleochemical time series. But rapid millennial-scale variability can be seen in cores from high accumulation rate series. Atlantic deep water chemical properties are seen to change in as little as a few hundred years or less. An extraordinary new 52.7-m-long core from the Bermuda Rise contains a faithful record of climate variability with century-scale resolution. Sediment composition can be linked in detail with the isotope stage 3 interstadials recorded in Greenland ice cores. This new record shows at least 12 major climate fluctuations within marine isotope stage 5 (about 70,000–130,000 years before the present).

(Table 2) Stable isotopes in foraminifers at DSDP Leg 78

Analyses of stable isotopes of monospecific planktonic foraminifers (G. quadrilobatus group) and monogeneric benthic foraminifers (Cibicidoides spp.) from late Neogene Atlantic Site 502 and Pacific Site 503 were conducted in order to determine the paleoceanographic changes resulting from the late Neogene uplift of the Panama Isthmus and from climatic cooling. In general, results at each site are similar to those from previous studies for the late Miocene and late Pliocene time interval, documenting the late Miocene (6 Ma) shift in carbon isotopes and the inferred growth of permanent Northern Hemisphere continental ice sheets beginning about 3.2 Ma. Comparison of Atlantic-Pacific planktonic-benthic isotope data for four stratigraphic intervals (~6-8, ~5-6, ~3-5, and ~2-3 Ma) suggests that increasing isolation of Atlantic and Pacific low-latitude waters may be related to the emergence of the Panama Isthmus. The contrast between Atlantic and Pacific benthic foraminiferal d13C increased in two steps from 0.60 per mil to 1 per mil (the modern contrast) at about 6 Ma and 3 Ma. The first increase (0.15 per mil) may represent the end of previously limited deep-water communication between the Atlantic and Pacific at the present location of Panama. The second increase (0.25 per mil) may be due to increased production of North Atlantic Deep Water. This probably reflects the development of modern deep-sea circulation. The d18O of planktonic foraminifers begins to increase in Atlantic Site 502 at 4.2 Ma and may reflect the increasing salinity of the North Atlantic Ocean arising from diminishing surface-water exchange across Panama. This increase is clearly shown by contrasting the d18O of Atlantic and Pacific planktonic foraminifers, as well as the d18O of planktonic and benthic foraminifers at Site 502. This inferred increase in surface-water salinity begins at the time of increasing provinciality of Atlantic and Pacific planktonic foraminifers.

Stable carbon and oxygen isotope composition of benthic foraminifera

Seventeen surface sediment samples from the North Atlantic Ocean off NE-Greenland between 76° and 81°N, and nine samples from the South Atlantic Ocean close to Bouvet Island between 48° and 55°S were taken with the aid of a Multiple Corer and investigated for their live (Rose Bengal stained) benthic foraminiferal content within the upper 15 cm of sediment. Preferentially endobenthic Melonis barleeanum, Melonis zaandami, and Bulimina aculeata as well as preferentially epibenthic Lobatula lobatula were counted from 1-cm-thick sediment slices each and analyzed for stable carbon and oxygen isotopic compositions of their calcareous tests. Live and dead specimens were counted and measured separately. The carbon isotopic composition of the foraminifera was compared to that of the dissolved inorganic carbon (DIC) of simultaneously sampled bottom water. During a period of one month, one station off NE-Greenland was replicately sampled once every week and samples were processed as above. Live specimens of Lobatula lobatula are confined to the uppermost two centimeters of sediment. Live specimens of Melonis spp. are found down to 8 cm within the sediment but with a distinct sub-surface maximum between 2 and 5 cm. The down-core distribution of live Bulimina aculeata shows a distinct surface maximum in the top centimeter and constant but low numbers down to 11-cm subbottom depth. The average stable carbon isotopic composition (d13C versus per mil PDB) of live Lobatula lobatula off NE-Greenland is by 0.4±0.1 per mil higher than the d13CDIC of the ambient bottom water at the time of sampling. There is evidence that this species calcify before the ice-free season, when bottom water d13CDIC is supposed to be higher. This would reconfirm the one-to-one relationship between d13C of ambient water DIC and cibicids, widely used by paleoceanographers. Live Melonis barleeanum show a negative offset from bottom water DIC of -1.7±0.6 per mil in the uppermost sediment and of -2.2±0.5 per mil in 3-4-cm subbottom depth. All d13C values of live Melonis spp. decrease within the upper four centimeters, regardless of the time of sampling and site investigated. The offset of live Bulimina aculeata from bottom water d13CDIC values of 8 stations rather constantly amounts to -0.6±0.1 per mil, no matter what subbottom depth the specimens are from. At one station however, where is strong indication of elevated organic carbon flux, the negative offset averaged over all sub-bottom depths increases to -1.5±0.2 per mil. Buliminids actively move within the sediment and by this either record an average isotope signal of the pore water or the signal of one specific calcification depth. The recorded signal, however, depends on the organic carbon flux and reflects general but site-specific pore water d13CDIC values. If compared with epibenthic d13C values from the same site, not influenced by pore water and related phytodetritus layer effects, Buliminad13C values bear some potential as a paleoproductivity proxy. Specimens of Melonis spp. seem to prefer a more static way of life and calcify at different but individually fix depths within the sediment. Although live specimens thus record a stratified pore water d13C signal, there is no means yet to correct for bioturbational and early diagenetic effects in fossil faunas.

Carbon geochemistry of sediments from the Amazon deep sea fan

Sediment cores from the Amazon deep sea fan recovered during R/V Meteor cruise 16-2 show in detail the modern areal distribution of sedimentary organic carbon, stable organic carbon isotopes of the organic matter (OM), as well as variations in the depositional processes. In addition, we studied up to 300 m long drilled sediment records recovered during ODP Leg 155 which allow evaluation of temporal variations on the Amazon fan. Our results reveal new evidence for a very rapid change of fan depositional processes and organic carbon source at times of sea-level change over the middle and lower Amazon fan. To estimate the amount of terrestrial organic carbon stored in sediments from the last glacial in the Amazon fan we used stable organic carbon isotopes of the OM (delta13Corg), organic carbon content (Corg), and age models based on oxygen isotopes, faunal data, and magnetic excursions. Following our results, the organic carbon accumulation on the Amazon deep sea fan is controlled by glacio-eustatic sea-level oscillations. Interglacial sea-level high stand sediments are dominated by marine OM whereas during glacial sea-level low stands terrestrial organic carbon is transported beyond the continental shelf through the Amazon canyon and deposited directly onto the Amazon deep sea fan. Glacial sediments of the Amazon fan stored approximately 73*10**15 g terrestrial Corg in 20,000 years or 3.7*10**12 g terrestrial Corg/yr (equivalent to 7-12% of the riverine organic carbon discharge; assuming constant paleo discharge), which is about the same amount of terrestrial organic carbon as deposited on the Amazon shelf today (3.1*10**12 g terrestrial Corg/yr or 6-10% of the modern riverine organic carbon discharge).

Stable hydrogen and carbon isotope records and concentration data for four long chain n-alkanes from core GIK16160-3 derived from the Zambezi delta in the Mozambique Channel during the last 37,000 years

Hydrogen isotope values (dD) of sedimentary terrestrial leaf wax such as n-alkanes or n-acids have been used to map and understand past changes in rainfall amount in the tropics because dD of precipitation is commonly assumed as the first order controlling factor of leaf wax dD. Plant functional types and their photosynthetic pathways can also affect leaf wax dD but these biological effects are rarely taken into account in paleo studies relying on this rainfall proxy. To investigate how biological effects may influence dD values we here present a 37,000-year old record of dD and stable carbon isotopes (d13C) measured on four n-alkanes (n-C27, n-C29, n-C31, n-C33) from a marine sediment core collected off the Zambezi River mouth. Our paleo d13C records suggest that each individual n-alkanes had different C3/C4 proportional contributions. n-C29 was mostly derived from a C3 dicots (trees, shrubs and forbs) dominant vegetation throughout the entire record. In contrast, the longer chain n-C33 and n-C31 were mostly contributed by C4 grasses during the Glacial period but shifted to a mixture of C4 grasses and C3 dicots during the Holocene. Strong correlations between dD and d13C values of n-C33 (correlation coefficient R2 = 0.75, n = 58) and n-C31 (R2 = 0.48, n = 58) suggest that their dD values were strongly influenced by changes in the relative contributions of C3/C4 plant types in contrast to n-C29 (R2 = 0.07, n = 58). Within regions with variable C3/C4 input, we conclude that dD values of n-C29 are the most reliable and unbiased indicator for past changes in rainfall, and that dD and d13C values of n-C31 and n-C33 are sensitive to C3/C4 vegetation changes. Our results demonstrate that a robust interpretation of palaeohydrological data using n-alkane dD requires additional knowledge of regional vegetation changes from which nalkanes are synthesized, and that the combination of dD and d13C values of multiple n-alkanes can help to differentiate biological effects from those related to the hydrological cycle.

Fatty acids and stable isotopes as indicators of early-life feeding and potential maternal resource dependency in the bull shark Carcharhinus leucas

The degree of reliance of newborn sharks on energy reserves from maternal resource allocation and the timescales over which these animals develop foraging skills are critical factors towards understanding the ecological role of top predators in marine ecosystems. We used muscle tissue stable carbon isotopic composition and fatty acid analysis of bull sharks Carcharhinus leucas to investigate early-life feeding ecology in conjunction with maternal resource dependency. Values of δ13C of some young-of-the-year sharks were highly enriched, reflecting inputs from the marine-based diet and foraging locations of their mothers. This group of sharks also contained high levels of the 20:3ω9 fatty acid, which accumulates during periods of essential fatty acid deficiency, suggesting inadequate or undeveloped foraging skills and possible reliance on maternal provisioning. A loss of maternal signal in δ13C values occurred at a length of approximately 100 cm, with muscle tissue δ13C values reflecting a transition from more freshwater/estuarine-based diets to marine-based diets with increasing length. Similarly, fatty acids from sharks >100 cm indicated no signs of essential fatty acid deficiency, implying adequate foraging. By combining stable carbon isotopes and fatty acids, our results provided important constraints on the timing of the loss of maternal isotopic signal and the development of foraging skills in relation to shark size and imply that molecular markers such as fatty acids are useful for the determination of maternal resource dependency.