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.     

Variations in the isotopic composition of molybdenum in freshwater lake systems

Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of ⁹⁷Mo/⁹⁵Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ⁹⁷Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ⁹⁷Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O₂ conditions in the bottom water through the Holocene indicates that increased O₂ concentrations are generally associated with low δ⁹⁷Mo/⁹⁵Mo values of the sediments, whereas lowered O₂ contents of the bottom water are accompanied by relatively high δ⁹⁷Mo/⁹⁵Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Discrimination of sulfur sources in pristine and polluted New Zealand river catchments using stable isotopes

An analysis of the S and O isotopic compositions and concentrations of dissolved S0₄ in river-and lake-water from 7 major catchments of the North and South Islands, New Zealand, allows the distinction between natural (geological, geothermal and volcanic) and anthropogenic S sources.The Buller and the Wairau, relatively pristine rivers in the South Island, show two end-member mixing between³⁴S- and¹⁸O-rich rain-water S0₄ (relatively enriched isotope values) and relatively depleted S0₄ from oxidation of bedrock sulfide. Tertiary sediments contribute the isotopically most depleted S (down to δ³⁴S_CDT−15‰) to the river-water S0₄, whereas Mesozoic greywacke contributes S with slightly positive δ³⁴S values. River-water S0₄δ¹⁸O_SMOW values range from 0 to + 5‰ most probably depending on the micro-environment of the oxidising zone. South Island rivers with S0₄δ³⁴S> + 5‰ have low S0₄ concentrations (< 3 mgl⁻¹) and are dominantly composed of rain-water S0₄ which is principally sea-water derived. In the North Island, the Hutt River S0₄ samples also lie on an isotopic mixing trend from “greywacke bedrock” to rain-water S0₄, the latter with δ³⁴S and δ¹⁸O values up to + 16 and + 6‰ respectively and a So₄/SO₄ + Cl fraction of 0.15 (sea-water is 0.12. Although dominated by greywacke, some samples in the Wairarapa area have relatively enriched δ¹⁸Sand δ³⁴S values and elevated S0₄ concentrations (up to 16 mgl⁻), together with higher SO₄/SO₄ + Cl fraction ratios. This suggests input of fertilizer S0₄ (δ³⁴S+ 17.2‰andδ¹⁸O+ 12.7‰) in the rivers of this agricultural area. The fertilizer loading of the Ruamahanga river can be estimated by its graphical offset from a deduced baseline for bedrockrainfall derived S0₄ on a S versus O isotope plot. The fertilizer loading represents about 20% of the S0₄ in the river. Extrapolation of this figure to the annual river discharge indicates that approximately 18% of the amount applied within the catchment is lost to the river.The source of the Whangaehu river is the Ruapehu crater lake (active volcano) with high S0₄ concentrations and very enriched S0₄ isotopic signatures (δ³⁴S> + 17‰andδ¹⁸O> + 12‰). Downstream this water is diluted by tributaries with lower S0₄ concentration and isotope signatures of Tertiary sediments similar to the rivers in the South Island. Both geothermal and rain-water S0₄ inputs to the streams flowing into Lakes Taupo and Rotorua were identified isotopically; in particular waters flowing out from Lake Rotorua have a higher geothermal derived S0₄ content than the inflows, indicating that there must be a considerable underwater geothermal input to the lake.     

Stable oxygen and carbon isotopes of carbonate concretions of the Miocene Yeonil Group in the Pohang Basin,Korea: Types of concretions and formation condition

Carbonate concretions in the Miocene sedimentary rocks of the Yeonil Group in the Pohang Basin (Korea) were investigated in terms of stable oxygen and carbon isotope composition to delineate the origin and associated diagenetic environment for their formation. Carbonate concretions are widely distributed in all the sedimentary rocks in the Pohang Basin, showing that the calcitic concretions are preserved within the mass-flow deposits and the dolomitic ones mostly in the hemipelagic siliceous rocks (diatomites). Concretions can be classified into four different types, on the basis of the stable isotopic signatures, each of which represents its own geochemical range.Type I concretions are calcitic and are composed of micrite to microspar. They occur in the conglomerates and sandstones which were deposited by mass flows (debris flow to turbidity current). It shows relatively lower δ¹⁸O (− 14.0 to − 9.3‰) and δ¹³C (− 19.6 to − 8.4‰) values. These concretions grew in a sulfate reducing zone under the influence of residual ambient seawater which had been significantly modified by volcanogenic sediments. Type II concretions are also calcitic, composed mostly of micrite with minor microspar and found in the sandstones. These concretions are characterized by relatively high δ¹⁸O (+ 1.8 to + 2.4‰) and variable δ¹³C (− 17.3 to − 0.4‰) values. These isotopic signatures reflect that Type II concretions formed from just beneath the sediment/water interface down to the sulfate reducing zone through the early stage of methanogenesis. Type III concretions are also calcitic, and composed largely of micrite with a minor contribution of microspar. They are observed in hemipelagic mudrocks which were deposited under the influence of mass flows. They are characterized by intermediate to high δ¹⁸O (− 4.6 to + 1.6‰) and high δ¹³C (− 1.3 to + 8.8‰) values. These concretions grew in a methanogenic zone by residual ambient seawater and/or seawater slightly modified by reaction with volcanogenic sediments. Type IV concretions are dolomite with calcite inclusion, and occur in hemipelagic siliceous rocks. These concretions are mostly composed of micrite and characterized by variable δ¹⁸O (− 9.1 to + 0.7‰) and high δ¹³C (+ 3.1 to + 17.9‰) values, suggesting formation in the methanogenic zone, although the residual ambient seawater is slightly modified by volcanogenic sediments.The same type of the concretions is widely distributed throughout the basin and always shows its own distinctive stable isotopic signature. This means that the formation of the given type depends upon the lithology and composition of host sediments that are closely related to the depositional process of the fan-delta systems regardless of their localities. Further, the different types of concretions are also found at the different, but closely spaced stratigraphic levels in the same locality, displaying the distinctive diagenetic conditions for each type. Such preservation of the unique diagenetic signatures in individual type of concretion suggests that the concretions formed in a completely closed diagenetic system. Therefore, caution should be made to simplify and generalize the diagenetic condition for the formation of any concretions in a large sedimentary basin.     

Sulphur isotope geochemistry of carbonatites

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

Distribution and isotope composition of nitrogen in Bay of Quinte (Lake Ontario) sediments

The concentrations and isotopic compositions of the various forms of nitrogen in silty clay sediments from the Bay of Quinte (Lake Ontario) have been determined. The total organic-N content is high throughout the sediment profiles and generally decreases with depth. On the contrary, exchangeable NH⁺₄-N concentration is quite low and tends to increase with depth in two out of three sediment cores examined. The concentration of non-exchangeable NH⁺₄-N and the 6 N HCl hydrolyzable NH⁺₄-N are relatively constant with depth. Among the N fractions analyzed, the exchangeable NH⁺₄-is most enriched in ¹⁵N. In most cases, the δ ¹⁵ N values of the N fractions remain relatively constant with sediment depth. There is no apparent correlation of δ ¹⁵ N values with the N concentration for any of the individual N fractions. The observed ranges in the δ ¹⁵ N values are: exchangeable NH⁺₄, + 5–+10‰; 6 N HCl hydrolyzable total N and 6 N HCl hydrolyzable NH⁺₄-N, + 3.5–+5.5‰.     

Stepwise enrichment of 15N along food chains: Further evidence and the relation between δ15N and animal age

The isotopic composition of nitrogen was measured in marine and fresh-water animals from the East China Sea, The Bering Sea, Lake Ashinoko and Usujiri intertidal zone. Primary producers, showed average δ¹⁵Nversus atmospheric nitrogen of +5.0%. (+3.4 to +7.5) in the Bering Sea and Lake Ashinoko, and +6.8%. (+6.0 to +7.6) in Usujiri intertidal zone. Blue green algae from the East China Sea show an average ?0.55%. (?0.8 to +1.2). All consumers, Zooplankton, fish and bird exhibited Stepwise enrichment of ¹⁵N with increasing trophic level. The ¹⁵N enrichment at a single feeding process ranged from +1.3 to +5.3 averaging +3.4 ± 1.1%.. This isotopic fractionation seems to be independent of habitat.The effect of age in animals was obtained by analyzing two marine mussels. The soft tissue nitrogen showed +2.0%. enrichment relative to that of primary producers, and the magnitude was almost constant with shell ages ranging from 0 to 8 years.A similar ¹⁵N enrichment occurs in all Molluscs, Crustaceans, Insecta, Amphibia, Fish, Ave and Mammal species regardless of the difference in the form of excreted nitrogen and in laboratory cultured fish, brine shrimp and mice (+2.9 to +4.9%.). The excreted ammonia from guppy was sufficiently light to balance the concentration of ¹⁵N to animal body.     

Investigation on the hydrodynamics of Ganga Alluvial Plain using environmental isotopes: a case study of the Gomati River Basin, northern India

An investigation using environmental isotopes (δ¹⁸O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ¹⁸O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ¹⁸O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ¹⁸O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ¹⁸O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.     

Geochemical Constraints on the Origin and Evolution of Spring Waters in the Changdu‐Lanping‐Simao Basin,Southwestern China

Chemical and isotopic data were measured for 51 leached brine springs in the Changdu-Lanping-Simao Basin (CD-LP-SM), China. The predominance of Cl and Na, saturation indices of carbonate minerals, and Na/Cl and Ca/SO4 ratios of ~1 suggest that halite, sulphate, and carbonate are the solute sources. Integration of geochemical, δ18O, and δD values suggests that springs are mainly derived from meteoric water, ice-snow melt, and water-rock interactions. B concentrations range from 0.18 to 11.9 mg/L, with δ11B values of ?4.37‰ to +32.39‰, indicating a terrestrial source. The δ11B-B relationships suggest B sources of crustal origin (marine carbonates with minor crust-derived volcanics); we did not identify a marine or deep mantle origin. The δ11B values of saline springs (+4.61‰ to +32.39‰) exceed those of hot (?4.37‰ to +4.53‰) and cold (?3.47‰ to +14.84‰) springs; this has contributed to strong water-rock interactions and strong saturation of dissolved carbonates. Conversely, the global geothermal δ11B-Cl/B relationship suggests mixing of marine and non-marine sources. The δ11B-Cl/B relationships of the CD-LP-SM are similar to those of the Tibet geothermal belt and the Nangqen Basin, indicating the same B origin. These differ from thermal waters controlled by magmatic fluids and seawater, suggesting that B in CD-LP-SM springs has a crustal origin.     

Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater

Isotopic composition of NO₃ (δ¹⁵N_NO3 and δ¹⁸O_NO3) and B (δ¹¹B) were used to evaluate NO₃ contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO₃. Combined use of these isotopes may be a useful tool in identifying NO₃ sources because NO₃ and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO₃ concentrations in residential parts of the study area is wastewater and not natural NO₃ or fertilizers. This is indicated by some samples with elevated NO₃ concentrations plotting along δ¹⁵N_NO3 and NO₃ mixing lines between natural NO₃ from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO₃ concentrations that fall along mixing lines between natural NO₃ and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO₃ sources in several wells because denitrification blurred the original isotopic signatures. The range of δ¹¹B values in native ground water in the study area (−8.2‰ to +21.2‰) is large. The samples with the low δ¹¹B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. δ¹¹B values from local STP effluent (−2.7‰) and wash water from a domestic washing machine (−5.7‰) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO₃ concentrations fell along mixing lines between wastewater and background water on plots of δ¹¹B against 1/B and Cl/B. Combined use of δ¹⁵N and δ¹¹B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized δ¹¹B value for background wells.     

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.     

Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

ABSTRACT

In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ¹⁵N_air (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ¹⁵N values (δ¹⁵N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ¹⁵N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ¹⁵N = + 2.1 to +3.6‰).

Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.     

Nitrogen Stable Isotopes of Macrophytes Assess Stormwater Nitrogen Inputs to an Urbanized Estuary

The ¹⁵N composition of seagrass and benthic macroalgae from shallow waters of Sarasota Bay was measured to determine if stable N isotopes can be used to trace stormwater N into macrophyte production within an urbanized estuary. Results show isotopically enriched macroalgae at the landward stations near creeks and bayous in the central Bay and in the southern portion of the Bay. A known sewage outfall at Whitaker Bayou resulted in δ ¹⁵NO₃ values from 0 to +9‰. Isotopically enriched NH₄ values in Phillippi Creek (+10 to +17‰) were similar to the stormwater ¹⁵NH₄ values from the watershed (+7 to +18‰). Enriched N sources supported a significant portion of macroalgae N demands in the southern reaches of the Bay while isotopically depleted N sources (i.e., atmospheric deposition and/or fertilizers) appear to be more important for macroalgae in the northern portion of the Bay. Macroalgae were typically more enriched than seagrass and appear to be better indicators of anthropogenic loadings near creeks and bayous that receive large volumes of stormwater and other anthropogenic N sources. Historically, studies have used enriched ¹⁵N in macrophytes to infer wastewater influences. This study shows that stormwater N inputs need to be considered in nitrogen budgets for aquatic systems that show anthropogenic ¹⁵N enrichment.     

2H/1H ratio of hopanes,tricyclic and tetracyclic terpanes in oils and source rocks from the Potiguar Basin,Brazil

We report the hydrogen isotope ratio ²H/¹H (expressed as δ²H values) of 8 selected hopanes, tricyclic and tetracyclic terpanes from oils and source rocks in the Potiguar Basin, and of associated formation water. Hopanes ranged in δ²H value from −79‰ to −142‰, whereas tri- and tetracyclic terpanes (TTTs) ranged from −137‰ to −225‰. Formation water δ²H values ranged from −23‰ to −32‰. The most significant pattern in the data is the systematic ²H enrichment of hopanes relative to TTTs, by an average of 45‰ in oils and 78‰ in source rock extracts. The hopanes appear close to hydrogen isotopic equilibrium with coeval formation water, whereas TTTs are significantly more ²H depleted. Given the similarities in structure between the two compound classes, it is unlikely that hopanes would be exchanged completely while the others would not. More likely, both classes have undergone a limited extent of exchange, but with the hopanes being biosynthesized with δ²H values closer to equilibrium. Our data suggest that at least some primary environmental and/or biotic information can be retained in the δ²H values of biomarkers in oils and extracts, and is not completely obscured by hydrogen exchange.     

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.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

The dynamics of central Main Ethiopian Rift waters: Evidence from δD, δO and Sr/Sr ratios

Water samples from cold and geothermal boreholes, hot springs, lakes and rivers were analyzed for δD, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr compositions in order to investigate lake water–groundwater mixing processes, water–rock interactions, and to evaluate groundwater flow paths in the central Main Ethiopian Rift (MER) of the Ziway–Shala basin. Different ranges of isotopic values were recorded for different water types: hot springs show δ¹⁸O −3.36 to +3.69 and δD −15.85 to +24.23, deep Aluto-Langano geothermal wells show δ¹⁸O −4.65 to −1.24 and δD −12.39 to −9.31, groundwater wells show δ¹⁸O −3.99 to +5.14 and δD −19.69 to +32.27, whereas the lakes show δ¹⁸O and δD in the range +3.98 to +7.92 and +26.19 to +45.71, respectively. The intersection of the Local Meteoric Water Line (LMWL: δD = 7 δ¹⁸O + 11.2, R² = 0.94, n = 42) and the Local Evaporation Line (LEL: δD = 5.63δ¹⁸O + 8, n = 14, R² = 0.82) was used to estimate the average isotopic composition of recharge water into the basin (δD = −5.15 and δ¹⁸O = −2.34). These values are depleted if compared with the modern-day average precipitation, presumably indicating paleo-groundwater components recharged during previous humid climatic phases. The measured stable isotope values indicate that the geothermal wells, some of the hot springs and groundwater wells mainly consist of meteoric water. The Sr isotopic signatures in all waters are within the range of the Sr isotopic composition of the rift basalts and rhyolites. The variability of Sr isotopic data also pinpoints complex water–rock interaction and mixing processes in groundwater and surface water. The ⁸⁷Sr/⁸⁶Sr ratio ranges from 0.70445 to 0.70756 in the hot springs, from 0.70426 to 0.70537 in two deep geothermal wells, and from 0.70673 to 0.70721 in the rift lakes Ziway, Langano, Shala and Awasa. The radiogenic composition recorded by the lakes indicates that the input water was predominantly affected by progressive interaction with rhyolitic volcanics and lacustrine sediments.     

Paleoenvironmental implications of taxonomic variation among δN values of chloropigments

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ¹⁵N values of chloropigments of photosynthetic organisms to determine the corresponding δ¹⁵N values of biomass - and by extension, surface waters - the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth’s history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N₂, NO₃⁻, and NH₄⁺ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ¹⁵N_biomass − δ¹⁵N_{chloropigment}) for prokaryotes, with average values for species ranging from −12.2‰ to +11.7‰. We define this difference as ε_por, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of ε_por reflect chloropigments that are ¹⁵N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of ε_por for freshwater cyanobacterial species is −9.8 ± 1.8‰, while for marine cyanobacteria it is −0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., ε_por values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of ε_por for eukaryotic algae (range = 4.7-8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of ε_por do not depend on the type of nitrogen substrate used for growth. The observed environmental control of ε_por suggests that values of ε_por could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.     

Reconstruction of Holocene paleohydrological and sedimentological characteristics of Umm Ar-Rimam basin (northern Kuwait)

The paleohydrological and sedimentological characteristics of a playa lake in northern Kuwait (Arabian Gulf) are reconstructed using sedimentological, geochemical, and isotopic techniques. The sequence consists of up to 8 cycles of S-poor, alluvial sediments capped by a thin organic soil interbedded with gravity-fall calcrete sediments. The succession is locally derived from mainly Quaternary sediments and is regressive with upsection filling of the subsiding basin by cycles of sheetwash flow in response to climatic change. There is no natural, open-water lake water as indicated by low total organic carbon (TOC) data, but the presence of incised calcrete yardangs suggests that more extensive open-water conditions were operative in the past. Stable isotope (δ¹⁸O‰ and δ¹³C‰) values of the authigenic carbonates indicate the following three distinct processes: evaporation, meteoric fluid infiltration, and rapid per-descensum flow (rapid downward movement of water and playa sediment through pipes) through a porous, clastic sequence. Because evaporites are scarce, other factors besides evaporation action control chemical and isotopic compositions of the per-decensum lake fluids. Consequently, the isotopic composition cannot be interpreted exclusively as an indicator of salinity or evaporation ratio. The degassing of CO₂ during groundwater discharge may explain the enriched carbon isotope values for the authigenic carbonates precipitated in the sediments. Hydrologically closed lake water bodies tend to show low negative carbonate oxygen and carbon isotopic signatures. Isotopically negative δ¹³C values imply a strong input of soil-zone carbon to the groundwater of the top 60 cm of the sediment. Lakes that are hydrologically closed and evaporate or equilibrate with atmospheric CO₂ will tend to have low negative δ¹⁸O and δ¹³C values in the carbonates as reported by Talbot (Chem Geol: Isotope Geosci Sect 80(4):261–279, 1990). Biologically active lakes will tend toward lower δ¹³C of dissolved carbon due to the photosynthetic effects of ¹²C withdrawal as reported by Dunagan and Driese (J Sed Res 69:772–783, 1999). Increased biological activity during sedimentation may account for low carbon isotope values where plants were abundant, but in shrinkage-dominated systems (those of clay-rich soil subjecting to wet-dry conditions), carbon isotopes will be largely inherited from the calcretic limestones in the land extending landward of the coast and not influenced by coastal processes (known as hinterland), such as Umm Ar-Rimam depression. This basin does not fit the classic shallow playa-type basins of the Arabian Peninsula but rather the recharge playas of the southwestern USA.