Examining the fate of WWTP effluent nitrogen using δ 15N–NH4 +, δ 15N–NO 3 − and δ 15N of submersed macrophytes

The use of submersed macrophyte tissue δ ¹⁵N to quantify the level of WWTP effluent use in a highly urbanized and agricultural river was evaluated using several methods. Macrophytes, NH₄ ⁺ and NO₃ ^? were collected by canoe along two 10 km reaches of river, upstream and downstream of two major municipal WWTPs over 3 years. NH₄ ⁺ decreased in concentration while δ ¹⁵N–NH₄ ⁺ increased as a function of distance downstream of both WWTPs, changing in one survey from 13 to 31 ‰ over 1 km. This increase is attributed to the combined effects of volatilization, nitrification and uptake. While NO ₃ ^? concentrations increased downstream of the WWTP over one of the survey reaches, δ ¹⁵N–NO ₃ ^? showed no prominent trend with distance at either. Macrophyte tissue δ ¹⁵N increased with distance downstream of both WWTPs, with a slope not significantly different from that of δ ¹⁵N–NH₄ ⁺ suggesting that macrophytes incorporate effluent NH₄ ⁺ as their main N source in those areas. However, mixing models suggest that towards the end of the reach, where source separation is distinct, macrophytes may utilize background NO ₃ ^? . Our study indicates the difficulty of deriving precise estimates of effluent use by macrophytes in a system where the δ ¹⁵N of the effluent changes rapidly. It also illustrates the utility of macrophytes in describing those changes where the effluent is too attenuated to allow for direct isotopic analysis.     

Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010,a total of 15 large tight gas fields have been found in China,located in the Ordos,Sichuan,and Tarim basins.The annual production and total reserves of these fields in 2010 were 222.5×108and 28657×108m3,respectively,accounting for 23.5%and 37.3%,respectively,of the total annual production and reserves of natural gases in China.They took a major part of all natural gas production and reserves in China.According to the analyses of 81 gas samples,the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics:(1)Plots of 13C1-13C2-13C3,13C1-C1/C2+3and 13C1-13C2demonstrate the coal-derived origin of tight gases in China;(2)For the primary alkane gases,both carbon and hydrogen isotopic values increase with increasing molecular mass,i.e.,13C113C213C313C4and2H12H22H3;(3)The isotopic differences of 13C2-13C1,13C3-13C1,2H2-2H1and 2H3-2H1decrease with increasing Ro(%)and C1/C1–4;(4)There are seven causes for the carbon and hydrogen isotopic reversal,however,the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.     

Influence of aquatic plants on the hydrogen isotope composition of sedimentary long-chain n-alkanes in the Lake Qinghai region,Qinghai-Tibet Plateau

The hydrogen isotopic composition(δD) of leaf wax long-chain n-alkanes(C27, C29, and C31) from lacustrine sediments has been widely applied to reconstruct terrestrial paleoclimatic and paleohydrological changes. However, few studies have addressed whether the aquatic-derived n-alkanes can affect the δD values of lake sedimentary long-chain n-alkanes, which are usually regarded as a recorder of the terrestrial hydrological signals. Here we systematically investigated δD values of long-chain n-alkanes from modern aquatic plants, both near-shore and off-shore surface sediments, surrounding terrestrial plant litters, as well as river water and lake water in Lake Qinghai and its satellite lakes on the northeastern Qinghai-Tibet Plateau. Our data showed that(i) δD values of long-chain n-alkanes from aquatic plants varied from-184‰ to-132‰ for n-C27, from-183‰ to-138‰ for n-C29, and from-189‰ to-130‰ for n-C31, respectively, with no significant differences among the three n-alkanes homologues;(ii) δD values of long-chain n-alkanes from aquatic plants were generally more positive than those from surrounding terrestrial plants, possibly because that they recorded the D-enrichment of lake water in this semi-arid region;(iii) δD values of long-chain n-alkanes from surface sediments showed significant differences among the three n-alkanes homologues, due to the larger aquatic input of n-C27 to the sedimentary lipid pool than that of n-C31, and(iv) n-C27 δD values of near-shore aquatic plants and near-shore sediments are more negative than those from off-shore as a result of lower δD values of near-shore lake water. Our findings indicate that in this region(i) the offset between sedimentary n-C27 and n-C31 δD values(ΔδDC27-C31) could potentially be used to evaluate if sedimentary long-chain n-alkanes are derived from a single source;(ii) while δD values of n-C27 may be influenced by lake water hydrological changes, sedimentary n-C31 is derived predominantly from terrestrial plants and thus its δD can serve as a relatively reliable indicator for terrestrial paleoclimatic and paleohydrological reconstructions.     

Stable carbon isotope signatures of cellulose in macrophytes collected from three eutrophic lakes in China

Aquatic plants are essential for maintaining the diversity and stability of a lake ecosystem. Stable carbon isotopes (δ¹³C) of macrophytes have been widely used as a powerful tool to study ecological processes and paleoenvironmental evolution in lakes. Varying results are obtained when using the δ¹³C of macrophytes to study the changes in the lake environment at different spatio-temporal scales. Thus, sample preparation and subsequent laboratory analyses are crucial for studying environmental changes using the isotopic signal retained in the macrophytes, and are essential for the interpretation of isotope-environment relationships. This study analyzed the δ¹³C of different tissue components of macrophytes in three lakes of the lower Yangtze River basin, and a correlation analysis was performed on aquatic environments influencing the δ¹³C values in the different tissue components of macrophytes. The test results showed the difference between the δ¹³C values of the whole sample and cellulose. Relative analyses indicated that the major factors contributing to the δ¹³C variability in macrophytes were pH and the concentration of dissolved inorganic carbon (DIC). The δ¹³C of α-cellulose (δ¹³C_AC) is more sensitive to environmental variables than that of the whole sample (δ¹³C_W) and holocellulose (δ¹³C_HC). The results of this study imply that extraction of α-cellulose is a prerequisite for research on the changes in lake environment using δ¹³C of macrophytes. This study aims to provide theoretical and data basis for further research on the environmental and ecological change using stable carbon isotopes of aquatic plants.     

老碳对水生态系统食物网的贡献

传统理论认为,支撑水生态系统食物网的碳主要来自于系统内部的初级生产者,如藻类、大型水生植物等,或者来自陆源输入的新鲜且容易分解的有机质;而部分生物或非生物生产的有机碳,在冰川、冻土等环境中可停留数百年至数千年(定义为老碳),由于储存环境稳定、物理化学性质顽固,难以参与水生生态系统有机碳循环.近年来这一观念不断被挑战.研究表明老碳能够参与水生态系统食物网碳循环:可以被微生物分解利用;被浮游动物、无脊椎动物直接或者间接摄取、或沿着营养级传递至鱼类、水禽等高级消费者.这意味着除了内部初级生产,老碳是支撑水生态系统重要的碳源.本文概述了当前老碳与水生态系统食物网关系研究最新进展和所取得的研究成果,介绍放射性14C同位素技术在水生态学领域的应用,同时提出研究中存在的问题以及未来研究应关注的方向,以期促进我国水生态系统碳循环研究的进一步发展.     

Habitat influences Pacific salmon (Oncorhynchus spp.) tissue decomposition in riparian and stream ecosystems

Decomposition incorporates organic material delivered by Pacific salmon (Oncorhynchus spp.) into aquatic and terrestrial ecosystems of streams where salmon spawn. We hypothesized that salmon tissue decomposition would be faster, and macroinvertebrate abundance and biomass higher, in terrestrial compared to aquatic habitats, and this would be reflected in the nutritional quality of the tissue. Salmon tissue in coarse-mesh bags was placed in four habitats [terrestrial: riparian (RIP), gravel bars (GRA); aquatic: stream sediment surface (STR), buried in sediments (BUR)] in four southeast Alaska watersheds. After 2 (RIP, GRA) or 4 (STR, BUR) weeks of decomposition, tissue dry mass, macronutrient content, and macroinvertebrate colonizer abundance and biomass were determined. Overall, tissue decomposition was rapid (mean k = 0.088 day^?1), while nutritional quality remained high based on elemental ratios (mean C:N = 4.9; C:P = 140; N:P = 30), and differed among habitats (Linear-mixed effects model p < 0.05). Macroinvertebrate assemblages colonizing carcasses were unique to each habitat, although Diptera generally dominated. In terrestrial habitats, the dominant macroinvertebrates were Sphaeroceridae (96 % of invertebrate abundance in RIP habitat) and Calliphoridae larvae (98 % in GRA habitat). In aquatic habitats, the dominant macroinvertebrates were Chironomidae (48 % in STR habitat) and Chloroperlidae (72 % in BUR habitat). Macroinvertebrate colonizer abundance and biomass were higher in RIP (mean 286 individuals and 22 mg g^?1) than in other habitats (mean 4 individuals and 3 mg g^?1) (Friedman p < 0.05). Rapid decomposition rates and high invertebrate biomass, combined with the high nutritional quality of tissue, suggest rapid incorporation of critical salmon nutrients and energy into both aquatic and terrestrial ecosystems.     

Stable isotopic compositions and controlling factors of precipitation and atmospheric vapour in the headwaters of the Shule River

Stable isotopic compositions of precipitation (δ¹⁸O_p, δ²H_p and d-excess_p) and atmospheric vapour (δ¹⁸O_v, δ²H_v and d-excess_v) with high spatial–temporal resolution are crucial in revealing hydrologic cycle. Based on the variation characteristics of δ¹⁸O_p/δ¹⁸O_v, δ²H_p/δ²H_v and d-excess_p/d-excess_v in the headwaters of the Shule River (HSR) on hourly and daily scales from June to September 2018, this study analysed the relationships between δ¹⁸O_p/δ²H_p and δ¹⁸O_v/δ²H_v combined with the equilibrium fractionation model, as well as δ¹⁸O_p/δ¹⁸O_v and meteorological factors. The slopes of local meteoric water line (LMWL) and the δ²H_v-δ¹⁸O_v fitting equation were similar (7.96 and 7.94) with both intercepts exceeding 10, reflecting the great contribution of recycling moisture. The values of δ¹⁸O_v/δ²H_v were lower than δ¹⁸O_p/δ²H_p but with consistent variation patterns throughout the period. The equilibrium simulation results suggested that precipitation and atmospheric vapour almost approached isotopic equilibrium state, especially during monsoon intrusion period. Affected by monsoon intrusion, the slopes and intercepts of the LMWLs and the δ²H_v-δ¹⁸O_v fitting equations were smaller than those during non-monsoon period and d-excess and δ¹⁸O were negatively correlated. Relative humidity had significant negative correlations with δ¹⁸O_p and δ¹⁸O_v in the whole period, however, the positive correlations between δ¹⁸O_p/δ¹⁸O_v and temperature were observed during non-monsoon and monsoon intrusion period, respectively. Our results demonstrated that precipitation and atmospheric vapour isotopic compositions exhibited consistency under the influence of diverse moisture sources, while more complex relationships were found between δ¹⁸O_p/δ¹⁸O_v and meteorological factors. This research provided evidence for using the isotopic compositions of atmospheric vapour to indicate moisture sources, and can improve understanding of the water cycle and eco-hydrological process from the perspective of the interaction between water and gas phases of the inland river basin in northwest China.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.     

Export and degassing of terrestrial carbon through watercourses draining a temperate podzolized catchment

We measured spatial and temporal variations in carbon concentrations, isotopic compositions and exports during a complete hydrological cycle in nine watercourses draining a lowland forested podzolized catchment, flowing into the Arcachon lagoon (France). In addition, integrated fluxes of CO₂ across the water-atmosphere interface were estimated to assess the relative importance of CO₂ evasion versus lateral carbon transport at the catchment scale. Watercourse similarities and specificities linked to the local catchment characteristics are discussed and compared with other riverine systems. Low concentrations of suspended particulate matter and particulate organic carbon (POC) were generally measured in all the watercourses (8.4 ± 3.4 and 1.6 ± 0.6 mg L^?1, respectively), reflecting limited mechanical soil erosion. The generally high POC content in the suspended matter (20 %), low Chl a concentrations (1.3 ± 1.4 μg L^?1) and the relatively constant δ¹³C-POC value (near ?28 ‰) throughout the year reveal this POC originates from terrestrial C₃ plant and soil detritus. The presence of podzols leads to high levels of dissolved organic carbon (DOC; 6.6 ± 2.2 mg L^?1). Similarly, high dissolved inorganic carbon (DIC) concentrations were measured in the Arcachon lagoon catchment (5.9 ± 2.2 mg L^?1). The δ¹³C-DIC value around ?20 ‰ throughout the year in many small watercourses reveals the predominance of terrestrial carbon mineralisation and silicate rock weathering in soils as the major DIC source. With pCO₂ between 1,000 and 10,000 ppmv, all watercourses were a source of CO₂ to the atmosphere, particularly during the low river stage. Organic carbon parameters remained relatively stable throughout the year, whereas DIC parameters showed strong seasonal contrasts closely linked to the hydrological regime and hyporheic flows. In total, the carbon export from the Arcachon watershed was estimated at 15,870 t C year^?1 or 6 t C km^?2 year^?1, mostly exported to the lagoon as DOC (35 %), DIC (24 %) and lost as CO₂ degassing to the atmosphere (34 %).     

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.     

Cross-taxon responses to elevated nutrients in European streams and lakes

Few studies have compared the response of different taxonomic groups to environmental stress across aquatic ecosystems. We regressed assemblage structure of fish, invertebrates, macrophytes, phytoplankton and benthic diatoms to total phosphorus concentration, after removing the effect of ecosystem size (stream order, lake surface area), using data from 66 streams and 45 lakes across Europe. In streams, the structure of benthic diatom assemblages, measured by nonmetric multidimensional scaling, showed the strongest correlation to elevated nutrient concentrations (adj. R² = 0.495), followed by benthic invertebrates (0.376), fish (0.181) and macrophytes (0.153). For lakes, the patterns were less clear: fish (0.155), macrophytes (0.146) and phytoplankton (0.132). Cross-system comparison showed that stream assemblages were responding more strongly to nutrient concentrations than lake assemblages. Moreover, our results lend some support to the conjecture that response signatures are related to trophic level, with primary producers (benthic diatoms) responding more strongly than consumers (invertebrates, fish). Knowledge of differences in responses among taxonomic groups and between habitats to disturbance can be used to design more cost-effective monitoring programs.     

Importance of aquatic macrophyte for invertebrate diversity in large subtropical reservoir

The abundance and preferences of individual invertebrate populations (including zooplankton) closely associated with the substrates provided by aquatic plant structures and open-water areas of Lake Nasser were quantified in this study in order to gain understanding of the importance of submerged macrophyte for invertebrate diversity, and their relation to water properties. The following water parameters were measured: temperature, pH, dissolved oxygen (DO), total dissolved salts, electrical conductivity, turbidity, total suspended solids, carbonate, bicarbonate, nitrate, nitrite, phosphate, sulphate, silica, potassium, total hardness, calcium and magnesium.Five macrophyte species were recorded: Myriopyllum spicatum, Najas horrida, Potamogeton schweinfurthii, Potamogeton pectinatus and Vallisneria spiralis. In total 67 invertebrate species were recorded, comprising 39 Rotifera, 12 Cladocera, 4 Copepoda, 4 Insecta, 2 Protozoa, 2 Ostracoda and one species of Turbellaria, Tardigrada, Annelida and Nematoda. Thirty-seven species were exclusively epiphytic, 11 species were collectively planktonic and 19 species were found in both habitats. The greatest abundance of epiphytic invertebrates occurred in association with N. horrida-P. schweinfurthii community.The results indicated that total suspended solids (TSS), TH and NO₂ are the most influential water variables on the distribution of the aquatic macrophyte samples and their invertebrate communities. Also, the study indicates that water variables have a higher impact on the aquatic macrophytes than on the associated invertebrate populations. P, NO₃, K, Na, Mg, Cl and DO were the most influential water variables that dictate the distribution of invertebrate groups recorded in the open-water zone. Water temperature, electric conductivity, pH, NO₂, SO₄⁻⁻, SiO₃⁻, CO₃⁻⁻ and turbidity have a lesser influence of the distribution of the invertebrates recorded in this zone.     

Re-assessing the nitrogen signal in continental margin sediments: New insights from the high northern latitudes

Organic and inorganic nitrogen and their isotopic signatures were studied in continental margin sediments off Spitsbergen. We present evidence that land-derived inorganic nitrogen strongly dilutes the particulate organic signal in coastal and fjord settings and accounts for up to 70% of the total nitrogen content. Spatial heterogeneity in inorganic nitrogen along the coast is less likely to be influenced by clay mineral assemblages or various substrates than by the supply of terrestrial organic matter (TOM) within eroded soil material into selected fjords and onto the shelf. The δ¹⁵N signal of the inorganic nitrogen (δ¹⁵N_inorg) in sediments off Spitsbergen seems to be appropriate to trace TOM supply from various climate- and ecosystem zones and elucidates the dominant transport media of terrigenous sediments to the marine realm. Moreover, we postulate that with the study of sedimentary δ¹⁵N_inorg in the Atlantic–Arctic gateway, climatically induced changes in catchment's vegetations in high northern latitudes may be reconstructed. The δ¹⁵N_org signal is primarily controlled by the availability of nitrate in the dominating ocean current systems and the corresponding degree of utilization of the nitrate pool in the euphotic zone. Not only does this new approach allow for a detailed view into the nitrogen cycle for settings with purely primary-produced organic matter supply, it also provides new insights into both the deposition of marine and terrestrial nitrogen and its ecosystem response to (paleo-) climate changes.     

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.     

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.     

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.     

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.     

The oxygen isotopic composition and temperature of Southern Ocean bottom waters during the last glacial maximum

We provide two new determinations of the oxygen isotopic composition of seawater during the last glacial maximum (LGM). High-resolution oxygen isotopic measurements were made on interstitial waters from Ocean Drilling Program (ODP) Sites 1168 and 1170 in the southeast Indian Ocean sector of the Southern Ocean. We use a diffusion-advection numerical model to calculate the glacial-interglacial change in bottom-water δ¹⁸O_sw from the pore water δ¹⁸O profiles; the first such determinations from this part of the oceans. Statistical analyses of the model runs indicate that Circumpolar Deep Water (CDW) δ¹⁸O_sw changed by 1.0-1.1±0.15‰ since the last glacial maximum (LGM). Our results are consistent with a previous calculation from a South Atlantic Southern Ocean location (ODP Site 1093) also situated within CDW. The new values determined in this study, together with previous estimates, are converging on a global average Δδ¹⁸O_sw of 1.0-1.1‰.Using the calculated bottom-water δ¹⁸O_sw, we have extracted the temperature component from the benthic foraminiferal δ¹⁸O record at Sites 1168 and 1170. Since the LGM, bottom waters at these two sites warmed by 2.6 and 1.9°C, respectively. The absolute temperature estimates for the LGM (−0.5°C [Θ=−0.6°C] at Site 1168 and −0.2°C [Θ=−0.4°C] at Site 1170) are slightly warmer than those reported from previous studies using the same technique, but are consistent with more homogenous deep-ocean temperatures during the LGM relative to the modern.     

Distribution of lead and thallium in the matrix of the Allende meteorite and the extent of terrestrial lead contamination in chondrites

Selective chemical dissolution has been used to study the distribution of Pb and Tl in an ultrafine ?20-μm matrix separate of Allende. The matrix was exposed to high-purity reagents ranging from H₂O, then HCl of increasing concentration and finally HF-HCl mixtures. A total of 17 extractions were obtained, each for a minimum period of 10 days. The isotopic compositions of the Pb released during the slow dissolution of the matrix fall into four distinct groups. The first, consisting of four extractions, released a component of terrestrial Pb isotopic composition with a total abundance of about 1 ppb. The next six extractions, which contained the bulk of the indigenous Pb and Tl corresponding to 96% and 94%, respectively, of the total matrix abundance, was of a reasonably homogeneous Pb isotopic composition with mean ratios of²⁰⁶Pb²⁰⁴Pb= 10.00and²⁰⁷Pb²⁰⁴Pb= 10.74. In the final seven extractions, the released Pb falls into two higher isotopic groupings and probably results from the dissolution of debris from chondrules and inclusions. The apparent age of the internal matrix isochron is4562 ± 14 My. The release of Pb and Tl shows a reasonable correlation with the matrix dissolution. This indicates that the Pb and Tl reside predominantly within the matrix phases rather than as a localised phase. The Tl isotopic composition of two matrix fractions and whole meteorite were measured and found to be indistinguishable from the terrestrial²⁰⁵Tl/²⁰³Tl ratio. Measurement of a terrestrial reagent standard in the range 1–10 ng Tl gave, for 20 analyses, a mean²⁰⁵Tl/²⁰³Tl ratio of2.38907 ± 0.00102 (2σ).The estimate of terrestrial Pb contamination is considerably lower than the 6–300 ppb assumed in some recent studies in order to explain the phenomenon of apparent excess radiogenic Pb in chondrites. The problem of terrestrial Pb pollution and the evidence which argues against a relatively severe and homogeneous Pb contamination of meteorites, is briefly considered. The apparent initial isotopic composition of the bulk of the indigenous Pb in the Allende matrix was found to be²⁰⁶Pb²⁰⁴Pb= 9.57and²⁰⁷Pb²⁰⁴Pb= 10.47. This is of a higher composition than the Pb in the Can?on Diablo troilite phase and further indicates that the phenomenon of apparent excess radiogenic Pb in chondrites is real.