Organic geochemical record of increased productivity in Lake Naukuchiyatal, Kumaun Himalayas, India

Organic geochemical proxies have been studied in a 45-cm-long core retrieved from Lake Naukuchiyatal in Kumaun Himalayas, India. Increase in TOC, N, hydrocarbons and pigments concentration from bottom to surface sediments of the core indicates increase in the lake productivity. Stable isotopes (δ¹³C and δ ¹⁵ N), biomarkers (TAR, CPI and n-ΣC_15,17,19) and C/N atomic (between 9 and 12) suggest dominance of algal derived organic matter in these sediments. Decrease in organic δ¹³C values (between ?27 and ?31‰) in surface sediments indicate influence of sewage and land runoff in shifting organic δ¹³C values, whereas low (between ?0.23 and 2.2‰) δ¹⁵N values together with high pigment concentrations (zeaxanthin and echinenone) represent dominance of cyanobacteria in the lake.     

Water and Organic Carbon Cycles in Monsoon-driven Humid Tropics of the Western Ghats Mountain Belt,India: Insights from Stable Isotope Approach

The Western Ghats form a major mountain belt, next to the Himalayas, in controlling the flux of water and carbon to the northern Indian Ocean. This study attempts to understand the water and carbon cycles in two humid tropical river basins with its streams originating at higher altitudes of the Western Ghats, India. Water and suspended particulate matter (SPM) were collected on a monthly scale during summer monsoon season (June-September) from Swarna and Nethravati rivers draining into the Arabian Sea. For the source apportionment, samples have been measured for stable isotopes of oxygen (δ¹⁸O) and hydrogen (δ²H) in water and stable isotopes of carbon (δ¹³C_POC) in particulate organic matter (POM) at spatial scale from tributaries and main channel of rivers, and runoff water from agricultural land (dominant paddy field) and forest in the downstream region. The association between δ¹⁸O and deuterium-excess in river water and rain water shows that water in these tropical basins depicts rainout effect of marine source moisture during the onset of summer monsoon. As the monsoon intensifies, the fresher rain water replenishes older water stored previously in sub surface soil layer leading to its flushing into the river during summer monsoon season. Stable carbon isotope ratio and elemental ratio of POM (δ¹³C_POC = -27.1 ± 0.4 ‰ and C/N = 8.1 ± 1.7) in two humid tropical river water during summer monsoon season is an admixture of suspended particulates from runoff water of forest (δ¹³C_POC = - 27.82 ± 0.4 ‰) and agricultural land (δ¹³C_POC = -26.29 ± 0.4 ‰). It is found that δ¹³C_POC shows minimal variability with SPM content and C/N ratio within the same organic carbon pool. The study emphasizes the need to consider the agricultural runoff contribution to the rivers while establishing the global elemental budget and observing the global climate change.     

Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ¹⁵N_bulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ¹⁵N_bulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ¹⁵N_ker), with offsets up to ～5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ¹⁵N of bulk rock and kerogen. The δ¹⁵N of sediments from the YF (δ¹⁵N_bulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ¹⁵N_bulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ¹⁵N_sil) were slightly lower than those of the δ¹⁵N_ker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N₂ loss leads to the relatively light δ¹⁵N_bulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ¹⁵N_bulk of rock and promotes the DNRA, resulting in heavy δ¹⁵N_ker and low δ¹⁵N_sil.     

Assessment of bacterial biomass in the highly contaminated urban Nanming River,Guiyang, SW China

High anthropogenic N loads and abundant bacteria are characteristic of highly contaminated urban rivers. To better understand the dispersal and accumulation of bacteria, we determined contents and isotopic compositions of suspended particulate organic matter (SPOM) and bacteria in a highly contaminated urban river (the Nanming) and effluents in winter and summer of 2013. Relative to SPOM, bacterial biomass in the river was depleted in ¹³C and ¹⁵N and its C/N ratio was lower (δ¹³C: ? 33.2‰ ± 3.1‰; δ¹⁵N: ? 1.5‰ ± 1.2‰; C/N: 4.8 ± 0.6), while effluents showed higher ¹³C and ¹⁵N contents and C/N ratios (δ¹³C: ? 25‰ ± 2.1‰; δ¹⁵N: + 8.5‰ ± 1.1‰; C/N: 8.1 ± 1.2). Source recognition of SPOM was based on carbon isotopes because they are conservative and distinct between end-members (effluent detritus and bacterial biomass). Using a mixing model, bacterial biomass in the river was calculated to account for < 20% and < 56% of bulk suspended particulate organic nitrogen in winter and summer, respectively. An N budget showed that bacterial N was a small proportion of total nitrogen (< 7.4%) in the riverwater.     

Isotope geochemistry of Swan Lake Basin in the Nebraska Sandhills,USA: Large 13C enrichment in sediment-calcite records

This study presents isotope geochemical analyses conducted on water column samples and core sediments collected from the Swan Lake Basin. Water analyses include the dissolved methane (CH₄) content and the ratio of carbon-13 to carbon-12 (δ¹³C) in dissolved inorganic carbon (DIC). The core sediments – sandy muds containing inorganic calcite, organic matter, and opal phases ± ostracods – were examined by X-ray diffraction, dated by radiocarbon (¹⁴C), analyzed for wt% organic carbon, wt% organic nitrogen, wt% organic matter, wt% calcite, δ¹³C of bulk-sediment insoluble organic matter (kerogen), ¹⁸O:¹⁶O ratio (δ¹⁸O) and δ¹³C of bulk and ostracod calcite. Of particular significance is the large enrichment in carbon-13 (δ¹³C = +4.5 to +20.4‰ V-PDB) in the calcite of these sediments. The ¹³C-enriched calcite is primarily formed from DIC in the water column of the lake as a result of the following combined processes: (i) the incorporation of ¹³C enriched residual carbon dioxide (CO₂) after partial reduction to CH₄ in the sediments and its migration into the water column-DIC pool; (ii) the preferential assimilation of ¹²C by phytoplankton during photosynthesis; (iii) the removal of ¹³C-depleted CH₄ by ebullition and of organic matter by sedimentation and burial. The ¹³C enrichment was low between 3624 and 2470 yr BP; high between 2470 and 1299 yr BP; and moderate since 1299 yr BP. Low ¹³C enrichment was formed under low water-column carbon levels while higher ones were formed under elevated rates of biomass and calcite deposition. These associations seem to imply that biological productivity is the main reason for carbon-13 enrichments.     

Hydrogen and carbon isotopes of petroleum and related organic matter

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Multi-stage fluid incursion in the Palaeozoic basement-hosted Saint-Salvy ore deposit (NW Montagne Noire,southern France)

The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H₂OCO₂(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ¹⁸O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H₂OCO₂NaClCaCl₂ fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl₂ content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ¹⁸O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ¹⁸O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ¹⁸O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ¹⁸O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ³⁴S_H2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ³⁴S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ¹³C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ³⁴S. Sphalerite has extremely low δ³⁴S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ³⁴S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ¹³C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.     

A Pilot Study of Trophic Level and Human Origins at the Xiaoshuangqiao Site, China (ca. 1400 BC) Using δD Values of Collagen

We present here a pilot study to examine trophic level effects and migration patterns at the middle Shang Dynasty site of Xiaoshuangqiao in Henan Province using δD results combined with δ13C and δ15N values. A total of 33 specimens (17 humans, 7 cattle, 5 pigs, 3 sheep, 1 dog) of bone collagen were isotopically analyzed for δ13C, δ15N, and dD values. A strong positive correlation (R2 = 0.94) between mean δ15N and δD values of herbivores (cattle and sheep), omnivores (pig), carnivores (dog) and humans was observed. The δD results were found to increase by ~10‰ to 20‰ from herbivores to omnivores to carnivorous, evidence that collagen δD results are a useful indicator for the study of trophic levels and dietary patterns at archaeological sites. The δD results were also used to examine the origins of two different groups of individuals buried at Xiaoshuangqiao. Individuals buried in sacrificial pits of district V had mean δD values (?47.0 ± 2.9‰, n = 11) that were significantly (p = 0.049) elevated compared to the people buried in the stratigraphy of district IX (?51.3 ± 3.3‰, n = 3), indicating that they were ingesting water from different locations. In addition, the D values of the people buried in the stratigraphy were similar to the pigs (?54.5 ± 4.2‰, n = 5) at Xiaoshuangqiao, suggesting that they were most probably of the local population, and that the individuals buried in the sacrificial pits were most possibly from the coast and prisoners of the Dongyi (“东夷”) people. Thus, δD results have the potential to examine human origins and migration patterns and should be increasingly used in conjunction with δ13C and δ15N values at archaeological sites.     

A 15 000‐year record of climate change in northern New Mexico,USA, inferred from isotopic and elemental contents of bog sediments

Elemental (C, N, Pb) and isotopic (δ¹³C, δ¹⁵N) measurements of cored sediment from a small bog in northern New Mexico reveal changes in climate during the Late Pleistocene and Holocene. Abrupt increases in Pb concentration and δ¹³C values ca. 14 420 cal. YBP indicate significant runoff to the shallow lake that existed at that time. Weathering and transport of local volcanic rocks resulted in the delivery of Pb‐bearing minerals to the basin, while a ¹³C‐enriched terrestrial vegetation source increased the δ¹³C values of the sedimentary material. Wet conditions developed over a 300 a period and lasted for a few hundred years. The Younger Dryas period (ca. 12 700–11 500 cal. YBP) caused a reduction in terrestrial productivity reflected in decreasing C/N values, δ¹⁵N values consistently greater than 0‰ and low organic content. By contrast, aquatic productivity increased during the second half of this period, evidenced by increasing δ¹³C values at the time of highest abundance of algae. Dry conditions ca. 8 000–6 000 cal. YBP were characterised by low organic carbon content and high Pb concentrations, the latter suggesting enhanced erosion and aeolian transport of volcanic rock. The range in δ¹³C, δ¹⁵N and C/N values in the sedimentary record fall within the range of modern plants, except during the periods of runoff and drought. The sedimentary record provides evidence of natural climate variability in northern New Mexico, including short‐ (multi‐centennial) and long‐(millennial) term episodes during the Late Pleistocene and Holocene. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterisation of chlorinated hydrocarbons from chlorine and carbon isotopic compositions: scope of application to environmental problems

A set of chlorinated hydrocarbons (TCE, PCE, DCM, 1,1,1-TCA, chloroform) provided by four manufacturers has been isotopically characterised for both C and Cl, using a new sensitive method. A very large range of δ¹³C (from −51.66 to −24.07‰/PDB) associated with a very large range of δ³⁷Cl (from −2.7 to +3.4‰/SMOC) was obtained. This range of δ³⁷Cl is much larger than that of inorganic Cl (±1‰ SMOC) and most individual solvents show a very distinct δ³⁷Cl compared to inorganic Cl isotopic signatures. Moreover, δ³⁷Cl/δ¹³C pairs are distinct from one solvent/manufacturer to another. In a δ¹³C versus δ³⁷Cl diagram, δ³⁷Cl / δ¹³C pairs show different trends for the products of a single manufacturer compared to another. This suggests that Cl isotopic compositions are probably highly fractionated during organic synthesis. The δ³⁷Cl values can be interpreted in terms of the probable manufacturing processes. Unlike the data published previously, with one exception, all the new results for samples reported here have positive δ³⁷Cl values which might differentiate natural Cl from that derived from degradation. This method has significant potential as a tool for investigating environmental pollution problems; in particular, it offers the possibility for validating models of transport and fate of pollutants.     

Stable chlorine and carbon isotope measurements of selected chlorinated organic solvents

Stable Cl and C isotope ratio results for 3 selected chlorinated solvents, perchloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) provided by 4 different manufacturers are presented. The isotope ratio for all compounds range between −3.5 and +6.0‰ forδ³⁷Cl and from −37.2 to −23.3%. forδ¹³C. The greatest³⁷Cl difference between manufacturers is observed in the TCE samples which showδ³⁷CI values of −2.5%o for PPG, +2.43‰ for ICI and +4.4‰ for DOW. TCAs show a smaller range (−2.4 to +2.0‰), while the TCEs have slightly different³⁷Cl contents. The¹³C data show the most distinctδ¹³C values for PCEs (−23.3 for DOW, −24.1 for Vulcan, −33.8 for PPG and −37.2‰ for ICI) while both TCEs and TCAs show a smallerδ¹³C range, but still distinct differences. These preliminary data suggest that each manufacturer and solvent type may have distinctiveδ⁶³⁷Cl andδ¹³C values. These results show that by using a combination of³⁷Cl and¹³C, there is a potential to indicate a specific source of chlorinated solvents, as well as an ability to delineate contamination episodes caused by these compounds in groundwaters.     

A dual-isotope approach to the nitrogen hydrochemistry of an urban aquifer

The potential for exploitation of urban aquifers is partly dependent on understanding the distribution and fate of urban N sources, such as sewage and fertilisers, that can limit the use of groundwater for public supplies. To investigate the application of the dual-isotope approach to understanding the N hydrochemistry of urban groundwater, this paper presents δ¹⁵N–NO₃⁻ and δ¹⁸O–NO₃⁻ data collected from two multi-level piezometers in the Sherwood sandstone aquifer beneath Nottingham in the English Midlands, UK. At one multi-level piezometer (Old Basford), depth sample measurements of δ¹⁵N–NO₃⁻ in the range +9.2 to +11.4 ‰ and δ¹⁸O–NO₃⁻ in the range +8.2 to +10.9‰, together with NO₃⁻ nitrate concentrations from 31.7 to 66.7 mg/l, are evidence for nitrification of sewage-derived inputs. In contrast, at the other multi-level piezometer (the Meadows), isotopically enriched samples (δ¹⁵N–NO₃⁻ in the range +24.3 to +42.2 ‰ and δ¹⁸O–NO₃⁻ in the range +20.5 to +29.4‰) are evidence for denitrification, although the compositional range of δ¹⁵N–NO₃⁻ does not identify the N source without corroborating data. For the Meadows location, a cross-plot of δ¹⁵N–NO₃⁻ versus δ¹⁸O–NO₃⁻ gave an enrichment of the ¹⁵N isotope relative to the ¹⁸O isotope by a factor of 1.9, within the range of 1.3–2.1 reported for denitrification in other studies. This study has shown that the dual-isotope approach provides improved understanding of N sources and fate in the urban environment but further work is required to identify nitrification pathways to provide more confidence in the application and interpretation of δ¹⁸O–NO₃⁻ measurements.     

The concentration and isotopic composition of hydrogen,carbon and nitrogen in carbonaceous meteorites

Concentrations and isotopic compositions were determined for H₂, N₂ and C extracted by stepwise pyrolysis from powdered meteorites, from residues of meteorites partially dissolved with aqueous HF, and from residues of meteorites reacted with HF-HCl solutions. The meteorites treated were the carbonaceous chondrites, Orgueil, Murray, Murchison, Renazzo and Cold Bokkeveld. Data determined for whole rock samples are in approximate agreement with previously published data. Acidification of the meteorites removed the inorganic sources of H₂, so that H₂ in the HF-HCl acid residues came primarily from insoluble organic matter, which makes up 70–80% fraction of the total carbon in carbonaceous meteorites. The δD in the organic matter differs markedly from previously determined values in organic matter in meteorites. The δD values of organic matter from acid residues of C1 and C2 carbonaceous chondrites range from +650 to + 1150%. The acid residues of the Renazzo meteorite, whose total H₂ has a δD of +930‰, gave a δD value of +2500‰. Oxidation of the HF-HCl residue with H₂O₂ solution removes the high δD and the low δ¹⁵N components. The δ¹³C values range between ?10 and ?21 and δ¹⁵N values range between +40 and ?11. The δ¹⁵N of Renazzo is unusual; its values range between +150 and ?190.There is good correlation between δD and the concentration of H₂ in the acid residues, but no correlation exists between δD, δ¹³C and δ¹⁵N in them. A simple model is proposed to explain the high δD values, and the relationships between δD values and the concentration of H₂. This model depends on the irradiation of gaseous molecules facilitating reaction between ionic molecules, and indicates that an increase in the rate of polymerization and accumulation of organic matter on grains would produce an increase in the deuterium concentration in organic matter.     

Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ¹³C values in CH₄ and CO₂ vary from ?59.5 to ?44.0‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO₂-HCO₃ system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO₃ ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy ¹³C isotope. The δ¹³C_TDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO₂, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ¹³C_TDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO₃ varies from 1–4 to 36–50 wt %. The δ¹³C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO₂ forms.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

Paleoclimatic interpretation of the past 30 ka from isotopic studies of the deep confined aquifer of the North China plain

The δ¹⁸O and δD values in the deep confined aquifer beneath the North China Plain which is located at 112°30′E–119°30′E and 34°46′N–40°25′N, reflect differences in paleoclimatic conditions between the Holocene and the late Pleistocene. Groundwater samples whose ¹⁴C ages are between 12 and 25 ka B.P have ranges of −9.4 to −11.7‰ for δ¹⁸O and −76‰ to −85‰ for δD values. These very negative δ¹⁸O and δD values reflect the cold and arid climate in the last glacial period. The temperature estimated in this period is 6–9 °C cooler than that of the present. The entire ranges of δ¹⁸O and δD values for samples with ¹⁴C dating from 7 ka B.P to present are −7.7‰ to −10.2‰ and −63‰ to −73‰, respectively. The greater δ¹⁸O and δD enrichments of these samples indicate a period of relatively humid and warm climate in the Holocene. However, the wide ranges of δ¹⁸O (−9.0‰ to −11.1‰) and δD (−66‰ to −80‰) values for samples with ¹⁴C age ranging from 12 to 7 ka B.P. imply an unstable climatic condition of rapidly increasing temperature, which marks the transition from the Pleistocene to the Holocene.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

Organic matter sources and transport in an agriculturally dominated temperate watershed

The quality, quantity, and origin of suspended organic matter were studied in the highly agricultural Upper Scioto River in Central Ohio. Late summer baseflow conditions were compared to late autumn high flow conditions. Variables examined in the suspended matter were the total suspended solids concentration, semi-quantitative concentrations of lignin, carbohydrate concentrations, total organic C, total and organic P, and δ-¹³C. Also examined were ratios of C to N, organic C to organic P ratios and fluxes of total organic C. The primary hypothesis of this research was that the quality (or biodegradability) and quantity of organic matter in the Upper Scioto River would increase during autumn stormflow conditions due to inputs of fresh terrestrial organic matter. The autumn suspended matter was also expected to reflect C4 plant contributions from corn organic matter. Results show that the quality and quantity of organic matter were greater during summer, as reflected in low molar ratios (178:1) of organic C to organic P, and higher organic C content of the suspended matter in summer. Summer suspended matter was 3.6% organic C and autumn suspended matter was 2.3% organic C. Carbon to N molar ratios in both seasons were very close to the Redfield ratio (6.6:1 in summer and 6.7:1 in autumn). Total suspended matter and total organic C concentrations were lower in autumn (8.7 mg/l⁻¹ TOC and 17.7 mg/l⁻¹ TSS) than in summer (17.5 mg/l⁻¹ TOC and 39.0 mg/l⁻¹ TSS), but the fluxes were greater in autumn due to greater stream flow. Stable isotope analyses suggested a phytoplankton or C3 plant source (most likely corn) for summer organic C (mean δ¹³C of −24.8‰) and a phytoplankton or C4 plant source for autumn organic matter (δ¹³C=−21.5‰).