Investigating the distribution and sources of organic matter in surface sediment of Coombabah Lake (Australia) using elemental,isotopic and fatty acid biomarkers

Extensive physical and biological measurements were made of the surface sediments within the shallow, semi-urbanised Coombabah Lake in southern Moreton Bay, Australia. Sediment bulk parameters (C/N ratios, δ¹³C and δ¹⁵N) and fatty acid biomarkers were used to determine distributions and sources of organic matter in the intertidal sediments. The determination of organic matter sources within coastal and estuarine settings is important in understanding the roles of organic matter as energy and nutrient sources. Spatial variability of biomarker values within the sediments were interpreted by thematic maps employing the Krigging algorithm. Grain size analysis indicated the lake was dominated by mud (<63 μm) in the southern (landward) and sand (>63 μm) in the northern (seaward) lake regions, respectively. Surface sediment organic C and N values ranged from 0.12% to 1.76% and 0.01% to 0.12% dry weight, respectively, and C/N ratios averaged 16.3±3.19%. Sedimentary δ¹³C values ranged from −26.1‰ to −20.9‰, with an average value of −23.9±1.0‰. Sedimentary δ¹⁵N values ranged from +1.7‰ to +4.8‰, with an average value of +2.8±0.8‰. Bulk sediment parameters suggested that sedimentary organic matter is provided predominantly by allochthonous sources in the form of fringing mangroves. Thirty-nine individual fatty acids were identified using gas chromatography–mass spectrometry. The mean contributions of long chain fatty acids (LCFAs), polyunsaturated fatty acids (PUFAs), saturated fatty acids (SAFAs) and bacterial fatty acids (BAFAs) were, respectively, 13.9±11.4%, 7.6±4.1%, 53.6±8.6% and 18.2±4.6% of the identified fatty acid methyl esters (FAMEs), with BAFAs occurring in all sampled sediments. Fatty acid compositions varied throughout lake sediments, which indicated spatial differences in autochthonous and allochthonous organic matter sources, including terrestrial and planktonic (i.e. zooplankton, diatoms and other algal species) sources. The contribution of organic matter from shoreline mangroves was confirmed by the presence of LCFAs and 18:2ω6 and 18:3ω3, which are markers for mangroves in this ecosystem. BAFAs were identified in increased proportions in sediments adjacent to urban developments and dominated by mud. Grain size was identified as a dominant factor in the fatty acid compositions and contributing values to FAME pool. Spatial patterns of C/N ratios, δ¹³C and δ¹⁵N values, and fatty acid biomarker contributions illustrated that there is a greater contribution of autochthonous and labile organic matter to the sedimentary organic matter pool in the northern (marine entrance) sediments compared to the more allochthonous sourced organic matter of the southern region of the lake. This study details the distribution and sources of organic matter within Coombabah Lake and illustrates the usefulness of a multiple biomarker approach in discriminating organic matter sources within estuarine environments.     

Differences in stable isotope compositions of freshwater snails from surface sediments of two Polish shallow lakes

The study reports and discusses the differences in δ¹³C and δ¹⁸O values of shells between several species of freshwater snails. Shells were derived from sediment samples collected from depths of 0.5, 1, 2 and 3 m along transects in two shallow eutrophic lakes located in mid-western Poland. Mean δ¹³C values of the shells ranged between −7.5 and −3.8‰ in Lake Jarosławieckie and between −8.1 and −5.2‰ in Lake Rosnowskie Duże, whereas mean δ¹⁸O values ranged between −2.2 and −0.2‰ and between −2.2 and 0.4‰ respectively in the studied lakes. A similar order of species in terms of shell isotope values, from least to most ¹³C and ¹⁸O-depleted was observed in both lakes and seems to indicate constancy of the factors controlling the stable isotope compositions of snail shells. We postulate that the nearly 4‰ difference in the mean carbon stable isotope values between the species was primarily controlled by the amount of metabolic carbon incorporated into the shells and the δ¹³C values of the snail food. Different growth cessation temperatures and microhabitats of the species studied result in temporally and spatially varied DIC δ¹³C values, water δ¹⁸O values and water temperature of shell precipitation, and may thus differentiate the δ¹³C and δ¹⁸O values of shells. The range of δ¹³C and δ¹⁸O values of individual shells from a sediment sample (mean 2.35 and 2.15‰, respectively) is interpreted as reflecting an intraspecific variability of isotope compositions in shells from a population and changes of the ambient conditions during the accumulation of the sediment layer. The species-specificity and intraspecific variability in C and O isotopic compositions of shells allow concluding that in palaeolimnological studies, stable isotope analyses should be performed on a set of mono-specific shells representing mean isotope compositions of the species for the interval studied rather than single shells or multispecific bulk shell material.     

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.     

Light carbon isotope events of foraminifera attributed to methane release from gas hydrates on the continental slope,northeastern South China Sea

In 2013, the China Geological Survey and Guangzhou Marine Geological Survey conducted the second Chinese gas hydrate expedition in the northern South China Sea(SCS) and successfully obtained visible gas hydrate samples. Five of the thirteen drilling sites were cored for further research. In this work, Site GMGS2-08 is selected for the stable isotopic analysis of foraminifera present in the boreholes in order to reveal the carbon isotopic characteristics of the foraminifera and their response to methane release in the gas hydrate geological system. Our results show that the methane content at Site GMGS2-08 is extremely high, with headspace methane concentrations up to 39300 μmol L~(-1). The hydrocarbon δ~(13)C values, ranging from-69.4‰ to-72.3‰ PDB, distinctly indicate biogenic generation. Based on the δD analytical results(~(-1)83‰ to~(-1)85‰ SMOW), headspace methane is further discriminated to be microbial gas, derived from CO_2 reduction. By isotopic measurement, five light δ~(13)C events are found in the boreholes from Site GMGS2-08, with foraminiferal δ~(13)C values being apparently lower than the normal variation range found in the glacial-interglacial cycles of the SCS. The δ~(13)C values of benthic Uvigerina peregrina are extremely depleted(as low as~(-1)5.85‰ PDB), while those of planktonic Globigerinoides ruber reach-5.68‰ PDB. Scanning electron micrograph(SEM) studies show that foraminiferal tests have experienced post-depositional alteration, infilled with authigenic carbonate, and the diagenetic mineralization is unlikely to be related to the burial depths. The correlation calculation suggests that the anaerobic oxidation of organic matter has only weak influences on the δ~(13)C composition of benthic foraminifera. This means that the anomalous δ~(13)C depletions are predominantly attributed to the overprinting of secondary carbonates derived from the anaerobic oxidation of methane(AOM). Furthermore, the negative δ~(13)C anomalies, coupled with the positive δ18O anomalies observed at Site GMGS2-08, are most likely the critical pieces of evidence for gas hydrate dissociation in the geological history of the study area.     

Evaluation of the carbon isotopic effects of NDIR and CRDS analyzers on atmospheric CO2 measurements

Non-dispersive infrared(NDIR) and cavity ring-down spectroscopy(CRDS) CO_2 analyzers use 12CO_2 isotopologue absorption lines and are insensitive to all or part of other CO_2-related isotopologues. This may produce biases in CO_2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO_2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO_2 mole fractions of the sample cylinders measured by G1301(CRDS) were in good agreement with those measured by Lo Flo(NDIR). The CO_2 values measured by both instruments were higher than that of a CO_2 isotope measured by G2201i(CRDS) analyzer for a test cylinder with depleted carbon isotopic composition δ~(13)C =-36.828‰, whereas no obvious difference was found for other two test cylinders with δ~(13)C=-8.630‰ and δ~(13)C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO_2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO_2 values calibrated by standard gases using Lo Flo and G1301 if the δ~(13)C and δ18O values are known.     

The distribution of13C in the Atlantic Ocean

Individual vertical profiles and north-south sections for the distribution of theδ¹³C of total dissolved inorganic carbon are presented for the Atlantic stations of the GEOSECS program. In most cases theδ¹³C data parallel the distribution of dissolved O₂. Differences are attributed to in-situ oxidation of organic matter and dissolution of particles of CaCO₃. Antarctic Bottom and Intermediate Waters have aδ¹³C value of near 0.5‰ relative to the PDB isotopic standard. The lowest values in the Atlantic ocean were found in the Antarctic Circumpolar waters which haveδ¹³C values as low as 0.2‰. The core of the North Atlantic Deep Water has aδ¹³C value of 1.0‰.     

Seasonal changes in the isotopic composition of planktonic foraminifera collected in Panama Basin sediment traps

Isotopic analyses have been made on five species of planktonic foraminifera collected in two deployments of PARFLUX Mark II time-series sediment traps in the Panama Basin. The automated sampling system on the traps provided 4 one-month samples from 29 July to 16 November 1979 and 6 two-month samples from December 1979 to November 1980.The δ¹⁸O values of Globigerinoides ruber and Globigerinoides sacculifer in this region are primarily affected by a low-salinity surface layer that forms during the early winter. These species each show a 1‰ total range in δ¹⁸O. The δ¹⁸O values of the colder-water species Globorotalia menardii, Neogloboquadrina dutertrei, and Globorotalia theyeri show smaller seasonal changes in δ¹⁸O. The δ¹³C values of G. ruber and G. sacculifer exhibit small seasonal changes (0.35 and 0.4‰ respectively) despite large seasonal changes in surface water productivity. The colder-water species exhibit only slightly larger changes in δ¹³C (up to 0.55‰) throughout the year. All colder-water species exhibit minimum or near minimum δ¹³C values during February and March, which is the period of maximum upwelling and primary productivity. Seasonal variations in the flux of foraminifera in the water column at this location will have only a small effect on the isotopic composition of the sediment assemblage; extreme values of δ¹⁸O and δ¹³C do not occur during the periods which are associated with the high flux of foraminiferal tests.     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

Nitrogen abundances and isotopic compositions in stony meteorites

Nitrogen contents range from a few parts per million in ordinary chondrites and achondrites to several hundred parts per million in enstatite chondrites and carbonaceous chondrites. Four major isotopic groups are recognized: (1) C1 and C2 carbonaceous chondrites have δ¹⁵N of+30to+50%.; (2) enstatite chondrites have δ¹⁵N of?30to?40‰; (3) C3 chondrites have low δ¹⁵N with large internal variations; (4) ordinary chondrites have δ¹⁵N of?10to+20‰. The major variations are primary, representing isotopic abundances established at the time of condensation and accretion. Secondary processes, such as spallation reactions, solar wind implantation and metamorphic loss may cause small but observable isotopic variations in particular cases. The large isotopic difference between enstatite chondrites and carbonaceous chondrites cannot be accounted for by equilibrium condensation from a homogeneous nebular gas, and requires either unusually large kinetic effects, or a temporal or spatial variation of isotopic composition of the nebula. Nitrogen isotopic heterogeneity in the nebula due to nuclear processes has not been firmly established, but may be required to account for the large variations found within the Allende and Leoville meteorites. The unique carbonaceous chondrite, Renazzo, has δ¹⁵N of+170%., which is well beyond the range of all other data, and also requires a special source. It is not yet possible, from the meteoritic data, to establish the mode of accretion of nitrogen onto the primitive Earth.     

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.     

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.     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than ?44‰, ?29‰ and ?26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \(C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than ?10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.     

Stable isotope paleohydrology and chemostratigraphy of the Albian Wayan Formation from the wedge-top depozone,North American Western Interior Basin

Understanding of the role of atmospheric moisture and heat transport in the climate system of the Cretaceous greenhouse world represents a major challenge in Earth system science.Stable isotopic paleohydrologic data from mid-Cretaceous paleosols in North America,from paleoequatorial to paleoArctic latitudes,have been used to constrain the oxygen isotope mass balance of the Albian hydrologic cycle.Over the range from 40°-50°N paleolatitude,sideritic paleosols predominate,indicating paleoenvironments with positive precipitation-evaporation(P-E)balances.Local exceptions occur on leeward side of the Sevier Orogen,where calcic paleosols in the wedge-top depozone record paleoenvironments with negative P-E balances in the orographic rain shadow.Stratigraphic sections in the Wayan Formation of Idaho(WF)were sampled from the wedge-top depozone.The units consist of stacked m-scale mudstone paleosols separated by m-scale sandstone-siltstone beds.Sections were sampled for organic carbon isotope profiles,and B-horizons from 6 well-developed paleosols were sampled for detrital zircons to determine maximum depositional ages.The first of these from the WF has produced a U-Pb concordia age of 101.0±1.1 Ma.This same WF section has produced a stratigraphic trend of upwardly decreasingδ~(13)C values ranging from-24‰upwards to-27‰VPDB,suggesting correlation to the late Albian C15 C-isotope segment.Pedogenic carbonates from the WF principally consist of micritic calcite,with carbon-oxygen isotope values that array along meteoric calcite lines(MCLs)withδ~(18)O values that range from-9.47‰up to-8.39‰VPDB.At approximately 42°N paleolatitude,these MCL values produce calculated paleoprecipitation values of-8.12‰to-7.04‰VSMOW,a range that is consistent with the estimates produced from other proxies at the same paleolatitudes across North America.These results indicate that despite the orographic rain shadow effect,the processes of meridional atmospheric moisture transport in this locale were similar to those in more humid mid-latitude paleoenvironments elsewhere in the continent.     

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.     

Methane Production and Isotopic Fingerprinting in Ethanol Fuel Contaminated Sites

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = −11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from −20‰ to −30‰, while the methane from toluene (δ¹³C = −28.5‰) had a carbon isotopic signature of −55‰. The field samples had δ¹³C values varying over a wide range (−10‰ to −80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded.     

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.     

Oxygen and carbon isotope evidence for seawater-hydrothermal alteration of the Macquarie Island ophiolite

Rocks of the Miocene Macquarie Island ophiolite, south of New Zealand, have oxygen and carbon isotopic compositions comparable to those of seafloor rocks. Basalt glass and weathered basalts have δ¹⁸O values at 5.8–6.0‰ and 7.9–9.5‰, respectively, similar to drilled seafloor rocks including samples from the Leg 29 DSDP holes near Macquarie Island. Compared to the basalt glass, the greenschist to amphibolite facies metaintrusives are depleted in¹⁸O (δ¹⁸O=3.2–5.9‰) similar to dredged seafloor samples, whereas the metabasalts are enriched (δ¹⁸O=7.1–9.7‰). Although the gabbros are only slightly altered in thin-section they have exchanged oxygen with a hydrothermal fluid to a depth of at least 4.5 km. There is an approximate balance between¹⁸O depletion and enrichment in the exposed ophiolite section. The carbon isotopic composition of calcite in the weathered basalts (δ¹³C=1.0–2.0‰) is similar to those of drilled basalts, but the metamorphosed rocks have low δ¹³C values (?14.6 to 0.9‰).These data are compatible with two seawater circulation regimes. In the upper regime, basalts were weathered by cold seawater in a circulation system with high water/rock ratios (?1.0). Based on calcite compositions weathering temperatures were less than 20°C and the carbon was derived from a predominantly inorganic marine source. As previously suggested for the Samail ophiolite, it is postulated that the lower hydrothermal regime consisted of two coupled parts. At the deeper levels, seawater circulating at low water/rock ratios (0.2–0.3) and high temperatures (300–600°C) gave rise to¹⁸O-depleted gabbro and sheeted dikes via open system exchange reactions. During reaction the seawater underwent a shift in oxygen isotopic composition (δ¹⁸O=1.0–5.0‰) and subsequently caused¹⁸O enrichment of the overlying metabasalts. In the shallower part of the hydrothermal regime the metabasalts were altered at relatively high water/rock ratios (1.0–10.0) and temperatures in the range 200–300°C. The relatively low water/rock ratios in the hydrothermal regime are supported by the low δ¹³C values of calcite, interpreted as evidence of juvenile carbon in contrast to the inorganic marine carbon found in the weathered basalts.     

Modern stable isotopic (δ18O, δ2H, δ13C) variation in terrestrial,fluvial, estuarine and marine waters from north‐central Sarawak,Malaysian Borneo

Stable isotope data on humid tropical hydrology are scarce and, at present, no such data exist for Borneo. Delta¹⁸O, δ²H and δ¹³C were analysed on 22 water samples from different parts of the Sungai (river) Niah basin (rain, cave drip, rainforest pool, tributary stream, river, estuary, sea) in north‐central Sarawak, Malaysian Borneo. This was done to improve understanding of the modern stable isotope systematics of the Sungai Niah basin, essential for the palaeoenvironmental interpretation of the Late Quaternary stable isotope proxies preserved in the Great Cave of Niah. The Niah hydrology data are put into a regional context using the meteoric water line for Southeast Asia, as derived from International Atomic Energy Agency/World Meteorological Organization isotopes in precipitation network data. Although the Niah hydrological data‐set is relatively small, spatial isotopic variability was found for the different subenvironments of the Sungai Niah basin. A progressive enrichment occurs towards the South China Sea (δ¹⁸O ?4·6‰; δ²H ?29·3‰; δ¹³C ?4·8‰) from the tributary stream (δ¹⁸O ?8·4‰; δ²H ?54·7‰; δ¹³C ?14·5‰) to up‐river (δ¹⁸O c. ?8‰; δ²H c. ?51‰; δ¹³C c. ?12‰) and down‐river values (δ¹⁸O c. ?7·5‰; δ²H c. ?45‰; δ¹³C c. ?11‰). This is thought to reflect differential evaporation and mixing of different components of the water cycle and a combination of depleted biogenic δ¹³C (plant respiration and decay) with enriched δ¹³C values (due to photosynthesis, atmospheric exchange, mixing with limestone and marine waters) downstream. Cave drip waters are relatively enriched in δ¹³C as compared to the surface waters. This may indicate rapid degassing of the cave drips as they enter the cave atmosphere. Copyright © 2005 John Wiley & Sons, Ltd.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

Oxygen isotope constraints on the origin and differentiation of the Moon

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of δ¹⁸O values (− 0.5 to 22.9‰) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; λ = 0.5259 ± 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Δ¹⁷O for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01‰ and are indistinguishable from the TFL. The δ¹⁸O values of high- and low-Ti lunar basalts are distinct. Average whole-rock δ¹⁸O values for low-Ti lunar basalts from the Apollo 12 (5.72 ± 0.06‰) and Apollo 15 landing sites (5.65 ± 0.12‰) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 ± 0.11‰). Evolved low-Ti LaPaz mare-basalt meteorite δ¹⁸O values (5.67 ± 0.05‰) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in δ¹⁸O do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine–pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average δ¹⁸O (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Δ=0.18‰) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the δ¹⁸O of lunar mantle olivine in this study are only 0.05‰ higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth–Moon system.