Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large¹⁵N/¹⁴N ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in¹⁵N by only 3‰ relative to the starting material (NH₃). The¹⁵N enrichment in polymers from the Miller-Urey reaction was 10–12‰. Both of these fractionations are small compared to the 80–90‰ differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.     

Stable calcium isotopic composition of meteorites and rocky planets

New measurements of mass-dependent calcium isotope effects in meteorites, lunar and terrestrial samples show that Earth, Moon, Mars, and differentiated asteroids (e.g., 4-Vesta and the angrite and aubrite parent bodies) are indistinguishable from primitive ordinary chondritic meteorites at our current analytical resolution (± 0.07‰ SD for the ⁴⁴Ca/⁴⁰Ca ratio). In contrast, enstatite chondritic meteorites are slightly enriched in heavier calcium isotopes (ca. + 0.5‰) and primitive carbonaceous chondritic meteorites are depleted in heavier calcium isotopes (ca. ? 0.5‰). The calcium isotope effects cannot be easily ascribed to evaporation or intraplanetary differentiation processes. The isotopic variations probably survive from the earliest stages of nebular condensation, and indicate that condensation occurred under non-equilibrium (undercooled nebular gas) conditions. Some of this early high-temperature calcium isotope heterogeneity is recorded by refractory inclusions (Niederer and Papanastassiou, 1984) and survived in planetesimals, but virtually none of it survived through terrestrial planet accretion. The new calcium isotope data suggest that ordinary chondrites are representative of the bulk of the refractory materials that formed the terrestrial planets; enstatite and carbonaceous chondrites are not. The enrichment of light calcium isotopes in bulk carbonaceous chondrites implies that their compositions are not fully representative of the solar nebula condensable fraction.     

Nitrogen contents and isotopic ratios of clasts from the enstatite chondrite Abee

Nitrogen contents and isotopic ratios have been determined for three clasts from the enstatite chondrite Abee by stepwise heating. The clasts possess a wide range in nitrogen content, ranging from 254 to 850 ppm, whereas the nitrogen isotopic ratios are nearly identical atδ¹⁵N= ?29.2±0.6‰. A refractory inorganic nitrogen-bearing phase contains about 90% of the nitrogen which is released at temperatures of 1000°C and above. The stepwise heating experiments suggest the possible existence of two other distinct nitrogen components, released at low (770°C) and high (1500°C) temperatures.     

Nitrogen and carbon isotopic composition in the diamonds of Mbuji Mayi (Zaïre)

The concentration and isotopic composition of nitrogen, measured in large diamonds (gram size) from the Mbuji Mayi kimberlite district (Zaïre) show a large range of variation (100<N<2100 ppm, ?11.2<δ¹⁵N< +6.0). The¹⁵N-depleted nitrogen is associated with the higher nitrogen concentrations. The large diamonds are individually rather homogeneous in¹³C (range ofδ¹³C < 0.9‰) while variations occur within small octahedral diamonds from the same district (range up to 5.8‰). The total range ofδ¹³C variation is about the same for the large diamonds (?10.5 <δ¹³C < ?5.5), the small octahedral diamonds (?10 <δ¹³C < ?4.6), and the carbonates from local kimberlites (?11.8 < δ¹³C < ?5.5). The diamond carbon isotopic data could indicate a complex story of crystallization within a deep-seated system fractionating its carbon isotopes.The nitrogen results indicate that nitrogen in diamonds is, on the average, markedly depleted in¹⁵N (weighted average ?5.15‰) relative to atmosphere, sediments and upper mantle.     

Zirconium isotope evidence for incomplete admixing of r-process components in the solar nebula

Isotopic anomalies in Mo and Zr have recently been reported for bulk chondrites and iron meteorites and have been interpreted in terms of a primordial nucleosynthetic heterogeneity in the solar nebula. We report precise Zr isotopic measurements of carbonaceous, ordinary and enstatite chondrites, eucrites, mesosiderites and lunar rocks. All bulk rock samples yield isotopic compositions that are identical to the terrestrial standard within the analytical uncertainty. No anomalies in ⁹²Zr are found in any samples including high Nb/Zr eucrites and high and low Nb/Zr calcium-aluminum-rich inclusions (CAIs). These data are consistent with the most recent estimates of <10⁻⁴ for the initial ⁹²Nb/⁹³Nb of the solar system. There exists a trace of isotopic heterogeneity in the form of a small excess of r-process ⁹⁶Zr in some refractory CAIs and some metal-rich phases of Renazzo. A more striking enrichment in ⁹⁶Zr is found in acetic acid leachates of the Allende CV carbonaceous chondrite. These data indicate that the r- and s-process Zr components found in presolar grains were well mixed on a large scale prior to planetary accretion. However, some CAIs formed before mixing was complete, such that they were able to sample a population of r-process-enriched material. The maximum amount of additional r-process component that was added to the otherwise well-mixed Zr in the molecular cloud or disk corresponds to ∼0.01%.     

The case for an unfractionated244Pu/238U ratio in high-temperature condensates

The coarse-grained, Ca-rich inclusions in the Allende meteorite are the highest-temperature condensates from the cooling solar nebula and, as such, the oldest solid objects in the solar system. All refractory elements with condensation points above the accretion temperature of the inclusions whose concentrations in them have been measured are seen to be present in the inclusions in unfractionated proportion to one another relative to C1 chondrites when data are averaged for a large number of inclusions. Observational data for U and theoretical data for both U and Pu suggest that these elements exhibited refractory behavior in the solar nebula. An experiment is proposed in which fissiogenic Xe and U contents are measured in a suite of these inclusions to obtain the²⁴⁴Pu/²³⁸U ratio of the solar system at the time of initial condensation with an uncertainty of ±15%.     

Lithium isotope composition of ordinary and carbonaceous chondrites, and differentiated planetary bodies: Bulk solar system and solar reservoirs

In order to better constrain the Li isotope composition of the bulk solar system and Li isotope fractionation during accretion and parent body processes, Li isotope compositions and concentrations were determined on a number of meteorite falls and finds. This is the first comprehensive study that systematically investigates a representative set of samples from carbonaceous chondrites (CI, CM2, CO3, CV3, CK4 and one ungrouped member), enstatite chondrites (EH, EL), ordinary chondrites (H, L, LL), and achondrites (one eucrite, diogenites, one pallasite, and a silicate inclusion from a IAB iron).

Carbonaceous chondrites have an average isotope composition of δ⁷Li = + 3.2‰ ± 1.9 (2σ) which agrees with the average composition of relatively pristine olivines (representative for the bulk composition) from the Earth primitive upper mantle (PUM). This is lighter than the average δ⁷Li of the basaltic differentiates of the Earth, Moon and Mars and the achondrites. It is an important observation, however, that the lighter end of the isotopic range of the differentiates always coincides with the averages of the mantle olivines and the carbonaceous chondrites. From this we conclude that the bulk of the inner solar system consists mostly of material from carbonaceous chondrites and that the variation seen in the differentiates is due to planetary body processes. Ordinary chondrites are significantly lighter than carbonaceous chondrites. No significant differences in δ⁷Li exist between enstatite chondrites (n = 3) and carbonaceous or ordinary chondrites. The difference between carbonaceous and ordinary chondrites and the variability within the chondrites could indicate the existence of distinct Li isotope reservoirs in the early solar nebula.     

Extraction of soluble collagen and its feasibility in the palaeodietary research

In current palaeodietary research, gelatinization is the main method to extract insoluble collagen(ISC) from ancient bones. However, the degradation products of ISC, i.e., soluble collagen(SC), is often neglected and abandoned. In this work, we try to separate the extracts of ancient bones using gel chromatography and compare the contents of carbon and nitrogen, atomic C/N ratio, and stable carbon and nitrogen isotopic values of the extracts from three peaks to determine which peak can be attributed to SC. At last, the potential application of SC in palaeodietary research is discussed based on the comparison of stable isotopic values between ISC and SC. Among the three peaks, the second with the retention time between 17.5 min and 27.5 min had the most broad peak shape, indicating that the molecular weights of proteins collected were most variable. Besides, the contents of carbon and nitrogen and atomic C/N ratio of extracts in this peak were closest to the corresponding ISC. Based on the above, we conclude that the extract in second peak is SC. More important, the δ 13C and δ 15N values of ISC and SC are very similar. For ISC and SC with atomic C/N ratios within the normal range(2.9–3.6), the mean difference of δ 13C value was only(0.3±0.2)‰(n=2) while δ 15N value was(0.6±0.1)‰(n=2). Although the atomic C/N ratios of some SC are slightly beyond the normal range, the mean differences of δ 13C and δ 15N values were still only(0.4±0.1)‰ and(0.3±0)‰(n=2) respectively. These isotopic differences are quite below the isotope fractionation in one trophic level(δ 13C values of 1‰–1.5‰ and δ 15N values of 3‰–5‰), suggesting that SC had great application potentials in palaeodietary research.     

Deuterium in carbonaceous chondrites

Hydrogen isotopic compositions in seven carbonaceous chondrites lie in the range ?70 to +771‰ relative to SMOW. These values decrease, to a range from ?145 to +219‰, after low-temperature oxidation in an oxygen plasma. Deuterium enrichment is therefore concentrated in the organic matter, the hydrous silicates probably lying close to the terrestrial range for such material. Calculated values for δD of the organic fraction are +450 ‰ for Orgueil and Ivuna and up to +1600‰ for Renazzo. These enrichments, at least for Orgueil and Ivuna, suggest equilibration with protosolar hydrogen at very low temperatures. Assuming a value of 2.5 × 10^?5 for the protosolar D/H ratio, nominal equilibration temperatures of 230°K for silicates and 180°K for organic matter may be derived.     

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.     

The solar Na/Ca and S/Ca ratios: A close comparison with carbonaceous chondrites

Solar abundances based on recent laboratory oscillator strengths confirm the relationship between solar matter and carbonaceous chondrites. Within spectroscopic uncertainties (typically±40%) these meteorites contain refractory and volatile elements in solar proportions. Significant improvement of accuracy at present seems restricted to a few abundant elements having reliable quantum-mechanical oscillator strengths, and necessitates strictly differential spectrum analysis. Taking this into account, the solar abundance ratios Na/Ca and S/Ca have been determined to an accuracy of±15%. The results are:Na/Ca= 0.91and S/Ca= 6.8. These volatile/refractory ratios just match type 1 carbonaceous chondrites, but contrast with other types.These and related interstellar abundance features place constraints on the condensation process and a potential heterogeneity of the solar nebula. There is evidence that no drastic pre-solar separation of interstellar gas and grains has occurred, but minor imbalance may be a common mechanism co-determining stellar metal content.     

Oxygen isotopic constraints on the origin of Mg-rich olivines from chondritic meteorites

Chondrules are the major high temperature components of chondritic meteorites which accreted a few millions years after the oldest solids of the solar system, the calcium–aluminum-rich inclusions, were condensed from the nebula gas. Chondrules formed during brief heating events by incomplete melting of solid dust precursors in the protoplanetary disk. Petrographic, compositional and isotopic arguments allowed the identification of metal-bearing Mg-rich olivine aggregates among the precursors of magnesian type I chondrules. Two very different settings can be considered for the formation of these Mg-rich olivines: either a nebular setting corresponding mostly to condensation–evaporation processes in the nebular gas or a planetary setting corresponding mostly to differentiation processes in a planetesimal. An ion microprobe survey of Mg-rich olivines of a set of type I chondrules and isolated olivines from unequilibrated ordinary chondrites and carbonaceous chondrites revealed the existence of several modes in the distribution of the ?¹⁷O values and the presence of a large range of mass fractionation (several ‰) within each mode. The chemistry and the oxygen isotopic compositions indicate that Mg-rich olivines are unlikely to be of nebular origin (i.e., solar nebula condensates) but are more likely debris of broken differentiated planetesimals (each of them being characterized by a given ?¹⁷O). Mg-rich olivines could have crystallized from magma ocean-like environments on partially molten planetesimals undergoing metal–silicate differentiation processes. Considering the very old age of chondrules, Mg-rich olivine grains or aggregates might be considered as millimeter-sized fragments from disrupted first-generation differentiated planetesimals. Finally, the finding of only a small number of discrete ?¹⁷O modes for Mg-rich olivines grains or aggregates in a given chondrite suggests that these shattered fragments have not been efficiently mixed in the disk and/or that chondrite formation occurred in the first vicinity of the breakup of these planetary bodies.     

87Rb-87Sr chronology of enstatite meteorites

A⁸⁷Rb-⁸⁷Sr analysis of some enstatite meteorites has been made. Whole rocks plot on an isochron of age 4.508 ± 0.037b.y. and strontium initial ratio 0.69880 ± 0.00044 (2σ errors; λ⁸⁷Rb= 1.42 × 10^?11yr^?1) . If the Norton County results are joined, we get an age of 4.516 ± 0.029b.y. and initial ratio of 0.69874 ± 0.00022. This result is indistinguishable from the whole rock isochron for H chondrites. It is interpreted as the age of condensation from the solar nebula. The identity of the⁸⁷Sr/⁸⁶Sr initial ratio with the ones for Allende white inclusions shows that this ratio was homogeneous in the solar nebula, and that the Rb-Sr fractionations observed between the different chondrite groups appeared only shortly before or during condensation accretion.Internal studies of the type-I enstatite chondrites Abee and Indarch and the intermediate-type Saint Mark's and Saint Sauveur have been done.Abee data scatter in the⁸⁷Rb-⁸⁷Sr diagram. For Indarch, Saint Mark's and Saint Sauveur, we obtained well-defined straight lines of “age” (T) and “initial ratio” (I): Indarch,T = 4.393 ± 0.043b.y.I = 0.7005 ± 0.0009; Saint Mark's,T = 4.335 ± 0.050b.y.I = 0.69979 ± 0.00022; Saint Sauveur,T = 4.457 ± 0.047b.y.I = 0.6993 ± 0.0014. Our result on Indarch agrees with the former result of Gopalan and Wetherill [5].A careful examination of the data shows that these straight lines are neither due to leaching effects by heavy liquids, nor result from terrestrial weathering. The “isochrons” for Indarch and Saint Sauveur can be mixing lines between enstatite and feldspar. The results are interpreted in terms of cosmochemical secondary effects: type-I and intermediate-type enstatite chondrites have been shocked 60–200 m.y. after their formation. This agrees with the idea of an early generalized bombardment of the inner solar system; this also indicates that type-I enstatite chondrites were rather situated in the outershells of their parent body and might be at the origin of the scatter of I-Xe ages of enstatite meteorites.Whole rock and enstatite from Bishopville, Cumberland Falls and Mayo Belwa have also been analysed. In these three aubrites, the⁸⁷Rb-⁸⁷Sr system is perturbed. Our Bishopsville sample might not be fresh and this makes the significance of our results uncertain. Cumberland Falls and Mayo Belwa probably suffered relatively recent shocks and open-system redistribution of Rb and Sr.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Organic carbon isotope gradient and ocean stratification across the late Ediacaran-Early Cambrian Yangtze Platform

Organic carbon isotope(δ13Corg) data from two well-preserved sections across a shallow-to-deep water transect of the late Ediacaran-Early Cambrian Yangtze Platform in South China show significant temporal and spatial variations. In the shallow-water Jiulongwan-Jijiapo section, δ13Corg values of the late Ediacaran Dengying Formation range from -29‰ to -24‰. In the deep-water Longbizui section, δ13Corg values from time-equivalent strata of the Dengying Formation are mostly between –35‰ and -32‰. These new data, in combination with δ13Corg data reported from other sections in South China, reveal a 6‰–8‰ shallow-to-deep water δ13Corg gradient. High δ13Corg values(-30‰) occur mostly in shallow-water carbonate rocks, whereas low δ13Corg values(-32‰) dominate the deep-water black shale and chert. The large temporal and spatial δ13Corg variations imply limited buffering effect from a large dissolved organic carbon(DOC) reservoir that was inferred to have existed in Ediacaran-Early Cambrian oceans. Instead, δ13Corg variations between platform and basin sections are more likely caused by differential microbial biomass contribution to total organic matter. High δ13Corg values(-30‰) documented from shallow-water carbonates are within the range of typical Phanerozoic δ13Corg data and may record the isotope signature of organic matter from primary(photosynthetic) production. In contrast, low δ13Corg values(-32‰) from deep-water sections may have resulted from higher chemoautotrophic or methanotrophic biomass contribution to bulk organic matter in anoxic environments. The δ13Corg data provide indirect evidence for ocean stratification and episodic chemocline fluctuations in the Ediacaran-Early Cambrian Yangtze Platform.     

Fractionation of sulfur isotopes by sediment adsorption of sulfate

Adsorption studies with sediment from the Bay of Quinte (Lake Ontario) indicate that the adsorption isotherm for sulfate concentration greater than 20 mg/l can be described by a Langmuir-type equation. The accompanying changes in δ³⁴S of the solutions range from +0.9 to +6.0‰ indicating enrichment of³²S in the sediments. The corresponding isotopic fractionation between the adsorbed sulfate and the sulfate remaining in solution ranges from ?10 to ?24‰, the larger fractionations being associated with low sulfate concentrations. The adsorbed sulfate is shown to significantly afftect the isotopic composition of the sediment in contact with the sulfate-bearing solution. The desorption of adsorbed sulfate is considered a possible mechanism for enriching natural freshwaters with³²S.     

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.     

Groundwater and surface water connectivity within the recharge area of Guarani aquifer system during El Niño 2014–2016

Recharge areas of the Guarani Aquifer System (GAS) are particularly sensitive and vulnerable to climate variability; therefore, the understanding of infiltration mechanisms for aquifer recharge and surface run‐off generation represent a relevant issue for water resources management in the southeastern portion of the Brazilian territory, particularly in the Jacaré‐Pepira River watershed. The main purpose of this study is to understand the interactions between precipitation, surface water, and groundwater using stable isotopes during the strong 2014–2016 El Niño Southern Oscillation event. The large variation in the isotopic composition of precipitation (from ?9.26‰ to +0.02‰ for δ¹⁸O and from ?63.3‰ to +17.6‰ for δ²H), mainly associated with regional climatic features, was not reflected in the isotopic composition of surface water (from ?7.84‰ to ?5.83‰ for δ¹⁸O and from ?49.7‰ to +33.6‰ for δ²H), mainly due to the monthly sampling frequency, and groundwater (from ?7.04‰ to ?7.76‰ for δ¹⁸O and from ?49.5‰ to ?44.7‰ for δ²H), which exhibited less variation throughout the year. However, variations in deuterium excess (d‐excess) in groundwater and surface water suggest the occurrence of strong secondary evaporation during the infiltration process, corresponding with groundwater level recovery. Similar isotopic composition in groundwater and surface water, as well as the same temporal variations in d‐excess and line‐conditioned excess denote the strong connectivity between these two reservoirs during baseflow recession periods. Isotopic mass balance modelling and hydrograph separation estimate that the groundwater contribution varied between 70% and 80%, however, during peak flows, the isotopic mass balance tends to overestimate the groundwater contribution when compared with the other hydrograph separation methods. Our findings indicate that the application of isotopic mass balance methods for ungauged rivers draining large groundwater reservoirs, such as the GAS outcrop, could provide a powerful tool for hydrological studies in the future, helping in the identification of flow contributions to river discharge draining these areas.     

Isotopic composition of precipitation during strong El Niño–Southern Oscillation events in the Southeast Region of Brazil

Equatorial Pacific sea surface temperature variations interact with processes of atmospheric circulation, creating conditions for the occurrence of El Niño–Southern Oscillation (ENSO). ENSO events represent the most important interannual phenomena affecting climate patterns worldwide and causing significant socio‐economic impacts. In the Brazilian territory, ENSO leads to an increase in drought episodes in the north‐eastern region and an increase in precipitation in the southern region, whereas the effects over the south‐east region are yet not well understood. The main goal of this study is to compare variations of isotopic composition in precipitation across the south‐east portion of the Brazilian territory during two very strong ENSO events: 1997–1998 (ENSO 1) and 2014–2016 (ENSO 2). Daily isotopic records, available from the Global Network of Isotopes in Precipitation database for ENSO 1, and samples collected during ENSO 2 were used to compare the influence of both events on the isotopic composition of precipitation. Seasonal variations indicated more depleted precipitation during the wet seasons (δ¹⁸O = ?5.4 ± 4.0‰) and enriched precipitation during the dry seasons (δ¹⁸O = ?2.8 ± 2.3‰). Observed rainfall variations were associated with atmospheric large‐scale processes and moisture transport from the Amazon region, whereas extreme values (enriched or depleted) appear to be associated with particular convective and stratiform precipitation events. Overall, more depleted isotopic composition of precipitation (δ¹⁸O = ?4.60‰) and higher d‐excess (up to +15‰) were observed during the dry season of ENSO 1 when compared with ENSO 2 dry season (δ¹⁸O‰ = ?2.80‰, d‐excess lower than +14‰). The latter is explained by greater atmospheric moisture content, particularly associated with recycling of transpiration fluxes from the Amazon region, during dry season of ENSO 1. No significant differences for δ¹⁸O and δ²H were observed during the wet season; however, d‐excess from ENSO 2 was greater than ENSO 1, due to the slightly greater atmospheric moisture content and very strong upward motion observed. Our findings highlight the opportunity that environmental isotopes offer towards understanding hydrometeorological processes, particularly, the evolution of extreme climatic events of global resonance such as ENSO.     

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.