δO of carbonate, quartz and phosphate from belemnite guards: implications for the isotopic record of old fossils and the isotopic composition of ancient seawater

Belemnite guards of Cretaceous and Jurassic age were found to contain varying amounts of quartz deposited both on the external surface and inside the rostrum. The oxygen isotopic composition of coexisting carbonate, quartz and phosphate from the same rostrum was measured according to well-established techniques. None of these compounds showed isotopic values in equilibrium with one another. Assuming δ¹⁸O values of the diagenetic water within the range of meteoric waters, the δ¹⁸O(SiO₂) yield temperatures in agreement with the apparent secondary origin of this phase. The δ¹⁸O(CO₃²⁻) range, with a certain continuity, between −10.8 and +0.97 PDB-1 with most of the intermediate values being within the range of the carbonate isotopic values of Mesozoic fossils. The most positive isotopic results obtained from phosphate are close to +23/+24‰ (V-SMOW). They can hardly be related to a secondary origin of the phosphate, or to the presence of diagenetic effects, since these results are among the most positive ever measured on phosphate. As far as we know there is no widespread diagenetic process determining an ¹⁸O enrichment of phosphate. The very low concentration of phosphate did not allow the determination of its mineralogical composition. All the available δ¹⁸O(PO₄³⁻) values from belemnite and non-belemnite fossils of marine origin of Tertiary and Mesozoic age are reported along with the newly measured belemnites. The following conclusions may be drawn from the data reported: (1) the pristine oxygen isotope composition of fossil marine organisms (either carbonate or phosphate) may easily undergo fairly large changes because of oxygen isotope exchange processes with diagenetic water; this process is apparent even in the case of geologically recent fossils; (2) the δ¹⁸O(PO₄³⁻) of belemnite rostra seems to be, at least in the case of the most positive results, in isotopic equilibrium with environmental water because of the similarity between the results from Cretaceous belemnites and the results from Cretaceous and Lower Tertiary pelecypods and fish teeth; 3) if so, the only feasible interpretation that can be suggested for the ¹⁸O enriched data is the possibility of a relatively large variation of the oxygen isotopic composition of ocean paleowater from Jurassic to recent time.     

Later Pleistocene/Holocene climate conditions of Qinghai-Xizhang Plateau (Tibet) based on carbon and oxygen stable isotopes of Zabuye Lake sediments

We present a time series of carbon and oxygen stable isotope records of the last 30?000 ¹⁴C years throughout the last glacial-postglacial cycle from western Qinghai-Xizhang (Tibet) Plateau. A 20-m core drilled in the south basin of Zabuye Salt Lake was analyzed for inorganic and organic carbon and total sulfur contents, δ¹³C and δ¹⁸O values of carbonates. Our results indicate that climatic changes have led to a drastic negative shift of stable isotope ratios at the transition between the Last Full Glacial and the postglacial phase during Later Pleistocene times (∼16.2 kyr BP), and a rapid positive shift at the transition from Pleistocene to Holocene (∼10.6 kyr BP). The first shift is marked by the drop of δ¹⁸O_carb values of about 10‰ (from +2 to −8‰) and δ¹³C_carb values of about 3‰ (from 5 to 2‰). The second shift which occurred at the transition from Pleistocene to Holocene was of similar magnitude but in the opposite direction. Isotope data, combined with total organic and inorganic carbon contents and the lithological composition of the core, suggest this lake was an alluvial pre-lake environment prior to ca. 28 ¹⁴C kyr BP. During ca. 28-16.2 ¹⁴C kyr BP, Zabuye Lake was likely a moderately deep lake with limited outflow. The cool and arid glacial climate led the lake level to drop drastically. Extended residence time overwhelmed the lower temperature and caused a steady increase of δ¹³C_carb and δ¹⁸O_carb values and total inorganic carbon content in the sediments. During ca. 16.2-10.6 ¹⁴C kyr BP, this lake probably overflowed and received abundant recharge from melting glaciers when the deglaciation was in its full speed. A spike of markedly enhanced δ¹³C_carb and δ¹⁸O_carb is seen at ∼11.5 kyr BP, probably due to the isotopic effects left behind by the short but severe Younger Dryas (YD) event. After ca. 10.6 ¹⁴C kyr BP, Zabuye Lake probably closed its surface outflow, due to strong desiccation and drastic climate warming. The Early and Middle Holocene were characterized by unstable climatic conditions with alternating warmer/cooler episodes as indicated by the severe fluctuations of total organic carbon, δ¹³C and δ¹⁸O values. A hypersaline salt lake environment was finally formed at Zabuye after ∼5 ¹⁴C kyr BP when the mirabilite and halite concentrations steadily increased and became the dominant minerals in the sediments. Severe imbalance of inflow/outflow resulted in the drastic increase of total sulfur, δ¹³C_carb and δ¹⁸O_carb values and dominance of halite in the lake since ca. 3.8 kyr BP to present.     

Mg isotopic composition of carbonate: insight from speleothem formation

Simultaneous high-precision measurement of ²⁴Mg, ²⁵Mg and ²⁶Mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry (MC-ICP-MS) relative to the international standard SRM980. Data are presented on low-Mg calcite speleothems and their associated host rocks and waters from four caves, one in the French Alps and three in Israel, covering various climate conditions. In addition, data are presented on three dolostones and three limestones from the Himalaya. The overall variation is 4.13‰ and 2.14‰ in δ²⁶Mg and δ²⁵Mg, respectively. This is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of Mg is not unique. Each speleothem shows a characteristic range of δ²⁶Mg values that are attributed to the isotopic composition of the local water. Differences between the isotopic composition of Mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to Mg isotopic fractionation during carbonate precipitation in the temperature range of 4-18°C. The low-Mg calcite is enriched in light isotopes by 1.35‰/AMU and the dependence on temperature has been found to be less than 0.02‰/AMU/°C. Despite various geological settings, the δ²⁶Mg of the studied dolostones is 2.0±1.2‰ higher than the δ²⁶Mg of the limestones. All together, these results suggest a strong mineralogical control and a weak temperature effect on the Mg isotopic composition of carbonate.     

Variations of O/O in plants from temperate peat bogs (Switzerland): implications for paleoclimatic studies

Despite the great potential of peat bogs as climatic archives, to date only few studies have focused on the climatic controls on cellulose isotopic composition in modern bog plants. This study attempts to calibrate plant-climate relationships by sampling a set of modern plant species (both vascular plants and mosses) and bog surface waters along an altitude transect in Switzerland. Isotopic analyses of water samples show that the δ¹⁸O-values of surface bog waters follow the trend of precipitation despite significant scatter in the data set. Detailed sampling of surface waters within one bog shows that δ¹⁸O-values vary widely and are closely related to the micro-topography of the bog surface. More enriched ¹⁸O/¹⁶O ratios in water samples collected from small raised hummocks than the ones collected from hollows are documented in both horizontal and vertical profiles. A δ¹⁸O-δD plot indicates that the process leading to the isotopic enrichment of the uppermost surface waters is evaporation, greater above Sphagnum covered hummocks than above open pools. To investigate the implications of such high variability of source water for plant α-cellulose δ¹⁸O-values, a detailed study of both surface water and α-cellulose δ¹⁸O-values within one site is conducted. The large δ¹⁸O variability observed in surface waters is found to be considerably smoothed in α-cellulose (by a factor of 5-10 depending on the plant species). This indicates that the water used by plant photosynthetic processes reflects the isotopic composition of the average annual precipitation. This points to a source water level for plants of a few decimeters where the variations are smaller than at the air-water interface. The response of the α-cellulose δ¹⁸O to the environmental gradient along the altitude transect varies considerably from species to species. For most of the species studied, the δ¹⁸O-values decrease with altitude, following the trends of δ¹⁸O-values in precipitation and in surface water samples. Some species, the cotton sedge Eriophorum vaginatum and the moss Sphagnum capillifolium, show statistically significant δ¹⁸O relationships to an altitude of −1.8‰/km and −2.9‰/km respectively. However, some other plant species, Calluna vulgaris, Vaccinium uliginosum, Andromeda poliflora, Carex pauciflora, Sphagnum cuspidatum and Sphagnum magellanicum, do not, or only partially, reflect changes in climatic parameters associated with an altitude increase. Furthermore, changes in relative humidity, which are not correlated with altitude, are found to explain a large part of the variability in δ¹⁸O-values for the sedge Carex pauciflora and the moss Sphagnum cuspidatum. Therefore, this study confirms the importance of species-specific studies when interpreting ¹⁸O/¹⁶O ratios of macrofossils along a fossil peat sequence as a record of past climate changes. Our study allows to extend the mechanistic model that isotopically links source water and cellulose to the physiological specificities of sedges and mosses. A comparison of the modeled and calculated net biological fractionation factors for Eriophorum vaginatum and Sphagnum capillifolium reveals that these two species appear to have a more homogeneous leaf reservoir than trees.     

Macroalgae blooms and δN in subtropical coastal lagoons from the Southeastern Gulf of California: Discrimination among agricultural, shrimp farm and sewage effluents

Macroalgae blooms of Gracilaria vermiculophylla, Hypnea spinella and Spyridia filamentosa have been found in coastal lagoons in the SE Gulf of California. Agriculture, livestock, shrimp and poultry farms and sewage contribute anthropogenic nitrogen to the systems. The δ¹⁵N of these sources, water column and macroalgae were studied in order to identify the N supply for macroalgae blooms. δ¹⁵N of three species of macroalgae (4.3-13.6‰) were enriched compared to the water column ( 3.7-6.8‰), probably because of fractioning from the macroalgae. δ¹⁵N of POM (1.4-10.3‰) was similar to the water column but the relationship was unclear. Depending on the site, macroalgae showed different δ¹⁵N values since some sites receive more or less influence from one given source of the associated watershed, which is reflected in the different δ¹⁵N values of the macroalgae of the same system and in the relative contributions of the sources.     

Oxygen isotope geochemistry of cherts from the Onverwacht Group (3.4 billion years), Transvaal,South Africa,with implications for secular variations in the isotopic composition of cherts

δ¹⁸O values for 87 chert samples from the 3.4-b.y.-old Onverwacht Group, South Africa, range from +9.4 to +22.1‰. δ-values for cherts representing early silicified carbonates and evaporites, and possible primary precipitates range from +16 to +22‰ and are distinctly richer in¹⁸O than silicified volcaniclastic debris and cherts of problematical origin. The lower δ-values for the latter two chert types are caused by isotopic impurities such as sericite and feldspar, and/or late silicification at elevated temperature during burial. Cherts with δ-values below +16‰ are thus not likely to yield geochemical data relevant to earth surface conditions.Fine-grained chert is less than 0.7‰ depleted in¹⁸O relative to coexisting coarse drusy quartz. Because coarse quartz preserves its isotopic composition with time, the maximum amount of post-depositional lowering of the δ-values of cherts by long-term isotopic exchange with meteoric groundwaters does not exceed 0.7‰ in 3.4 b.y. In response to metamorphism the δ-values of Onverwacht cherts appear to remain unchanged or to have increased by as much as 4‰. Neither metamorphism nor long-term isotopic exchange with groundwaters can explain why Onverwacht cherts are depleted in¹⁸O relative to their Phanerozoic counterparts.Meteoric waters with a δ¹⁸O range of at least 3‰ appear to have been involved in Onverwacht chert diagenesis. δ-values for possible primary cherts or cherts representing silicified carbonates and evaporites are compatible with the depositional and diagenetic environments deduced from field and petrographic evidence. Onverwacht cherts appear to have formed with δ-values at least 8‰ lower than Phanerozoic cherts.The new Onverwacht data combined with all published oxygen isotope data for cherts suggest a secular trend similar to that initially suggested by Perry (1967) in which younger cherts are progressively enriched in¹⁸O. However, Precambrian cherts appear to be richer in¹⁸O than Perry's original samples and can be reasonably interpreted in terms of declining climatic temperatures from ～70°C at 3.4 b.y. to present-day values, as initially suggested by Knauth and Epstein (1976). This surface temperature history is compatible with existing geological, geochemical, and paleontological evidence.     

Orographic distillation and spatio‐temporal variations of stable isotopes in precipitation in the North Atlantic

Little is known about the spatial and temporal variability of the stable isotopic composition of precipitation in the North Atlantic and its relationship to the North Atlantic Oscillation (NAO) and anthropogenic climate change. The islands of the Azores archipelago are uniquely positioned in the middle of the North Atlantic Ocean to address this knowledge gap. A survey of spatial and temporal variability of the stable isotope composition of precipitation in Azores is discussed using newly presented analyses along with Global Network of Isotopes in Precipitation data. The collected precipitation samples yield a new local meteoric water line (δ²H = 7.1 * δ¹⁸O + 8.46) for the Azores region and the North Atlantic Ocean. The annual isotopic mean of precipitation shows a small range for the unweighted and precipitation mass‐weighted δ¹⁸O‐H₂O values. Results show an inverse relation between the monthly δ¹⁸O‐H₂O and the amount of precipitation, which increases in elevation and into the interior of the island. Higher amounts of precipitation (from convective storm systems) do not correspond to the most depleted values of stable isotopes in precipitation. Precipitation shows an orographic effect with depleted δ¹⁸O‐H₂O values related to the Rayleigh effect. Monthly δ¹⁸O‐H₂O values for individual precipitation sampling stations show little relationship to air temperature. Results show a local source of moisture during the summer with the characteristics of the first vapour condensate. The stable isotope composition of precipitation is strongly correlated to the NAO index, and δ¹⁸O‐H₂O values show a statistically significantly trend towards enrichment since 1962 coincident with the increased air temperature and relative humidity due to climate change. Results are in line with observations of increasing sea surface temperature and relative humidity.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

Spatial variation of isotope composition in precipitation in a tropical environment: a case study from the Deduru Oya river basin,Sri Lanka

The stable isotope composition (¹⁸O and ²H) in the tropical precipitation collected from 18 locations throughout the Deduru Oya river basin in Sri Lanka, has been studied during August and September 2001, in order to characterize the isotopic composition of precipitation in the dry and intermediate climatic zones of Sri Lanka. The isotope compositions are described with respect to the distance from the coast and the altitude. The analyses show that δ¹⁸O vary from ? 5·11 to 1·39‰ and δD vary from ? 35·71 to 12·55‰. The d‐excess values range from ? 0·65 to 13·17 with an average value of ～7. Regression for the δ¹⁸O ? δD is y = 6·8x + 4·9 (R² = 0·9) which is compatible with the precipitation in other tropical regions. The lower slope in the regression line and the lower d‐excess value indicate high temperature events which were possibly aided by concentration through successive evaporation within the atmosphere. The spatial variation of isotope composition indicates two different cloud contributions for the rain events, of which one may be linked to the Indian Ocean contribution and the other to the high altitude condensation. Copyright © 2008 John Wiley & Sons, Ltd.     

Nitrogen cycling in the German Bight (SE North Sea) — Clues from modelling stable nitrogen isotopes

Nitrogen isotope values (δ¹⁵N) of surface sediments in the German Bight of the North Sea exhibit a significant gradient from values of 5–6‰ of the open shelf sea to values above 11‰ in the German Bight. This signal has been attributed to high reactive N (N_r) loading enriched in ¹⁵N from rivers and the atmosphere. To better understand the processes that determine the intensity and spatial distribution of δ¹⁵N anomalies in surface sediments, and to explore their usefulness for reconstructions of pristine N-input from rivers, we modeled the cycling of the stable isotopes ¹⁴N and ¹⁵N in reactive nitrogen through the ecosystem of the central and southern North Sea (50.9–57.3°N, 3.4°W−9.2°E) for the year 1995. The 3D-ecosystem model ECOHAM amended with an isotope-tracking module was validated by δ¹⁵N data of surface sediments within the model domain. A typical marine value (δ¹⁵N_nitrate=5‰) was prescribed for nitrate advected into the model domain at the seaside boundaries, whereas δ¹⁵N_nitrate of river inputs were those measured bi-monthly over 1 year; δ¹⁵N values of atmospheric deposition were set to 6‰ and 7‰ for NO_x and NH_y, respectively. The simulated δ¹⁵N values of different nitrogen compounds in the German Bight strongly depend on the mass transfers in the ecosystem. These fluxes, summarized in a nitrogen budget for 1995, give an estimate of the impacts of hydrodynamical and hydrological boundary conditions, and internal biogeochemical transformations on the nitrogen budget of the bight.     

Using stable isotopes of surface water and groundwater to quantify moisture sources across the Yellow River source region

Characterization of stable isotope compositions (δ²H and δ¹⁸O) of surface water and groundwater in a catchment is critical for refining moisture sources and establishing modern isotope–elevation relationships for paleoelevation reconstructions. There is no consensus on the moisture sources of precipitation in the Yellow River source region during summer season. This study presents δ²H and δ¹⁸O data from 111 water samples collected from tributaries, mainstream, lakes, and groundwater across the Yellow River source region during summertime. Measured δ¹⁸O values of the tributaries range from ?13.5‰ to ?5.8‰ with an average of ?11.0‰. Measured δ¹⁸O values of the groundwater samples range from ?12.7‰ to ?10.5‰ with an average of ?11.9‰. The δ¹⁸O data of tributary waters display a northward increase of 1.66‰ per degree latitude. The δ¹⁸O data and d‐excess values imply that moisture sources of the Yellow River source region during summertime are mainly from the mixing of the Indian Summer Monsoon and the Westerlies, local water recycling, and subcloud evaporation. Analysis of tributary δ¹⁸O data from the Yellow River source region and streamwater and precipitation δ¹⁸O data from its surrounding areas leads to a best‐fit second‐order polynomial relationship between δ¹⁸O and elevation over a 4,600 m elevation range. A δ¹⁸O elevation gradient of ?1.6‰/km is also established using these data, and the gradient is in consistence with the δ¹⁸O elevation gradient of north and eastern plateau. Such relationships can be used for paleoelevation reconstructions in the Yellow River source region.     

Hydrological conditions over the western Mediterranean basin during the deposition of the cold Sapropel 6 (ca. 175 kyr BP)

A new oxygen isotope record is reported from a stalagmite collected in the Argentarola Cave located on the Tyrrhenian coast of Italy. As shown from observations and numerical modeling of δ¹⁸O in modern precipitation, the recorded δ¹⁸O variability for this zone is dominated by the amount of precipitation (so-called ‘amount effect’). The δ¹⁸O profile measured in the stalagmite is characterized by a prominent negative excursion (ca. 2-3‰) between 180 and 170 kyr BP. This paleoclimatic feature is interpreted as being due to a relatively wet period which occurred during the penultimate glacial period, more precisely, during Marine Isotope Stage 6.5. This pluvial phase is shown to correspond chronologically to the deposition of the sapropel event 6 (S6). Although this particular sapropel event occurred during a cold phase, the δ¹⁸O excursion is similar to those corresponding to other sapropels (S4, S3 and S2). The evidence for humid conditions during S6 in the western Mediterranean basin agrees with previous studies based on deep-sea sediment cores. Taken collectively, the data suggest that during sapropel events dilution of ocean surface waters was not restricted to the output of the river Nile but was rather widespread over the entire Mediterranean Sea due to increased rainfall.     

Variations of δ<Superscript>18</Superscript>O in Rivers of Crimea in Winter

The results of studies of variations of δ¹⁸O values in river water in Crimea Peninsula in January–February 2015–2017 are given. The variation range of δ¹⁸О in river water over the three years of studies never exceeded 3‰. A tendency toward an increase in δ¹⁸О in the water of the Salgir, Kacha, Al’ma, Bel’bek, Biyuk-Karasu from their sources to mouths was identified and explained by a decrease in evaporation in the mouth areas of the rivers relative to their sources and upper reaches, and the inflow of isotopically light precipitation (rain and snow) into the rivers in their upper reaches. The values of δ¹⁸О in waters of the rivers with regulated stream were found to increase under the effect of the Simferopol Reservoir on the Salgir River and the Izobil’nenskoe Reservoir on the Ulu-Zen’ River. The values of δ¹⁸О in the upper reaches of the large rivers of Kacha and Bel’bek (the northwestern slope of the Crimean Mountains) vary from ?8.7 to ?9.7‰, except for the rivers of Al’ma (?7.7‰) and Kokozka (?10.2‰) because of the different shares of groundwater in the recharge of these rivers.     

Moisture origin and stable isotope characteristics of precipitation in southeast Siberia

The paper presents oxygen and hydrogen isotopes of 284 precipitation event samples systematically collected in Irkutsk, in the Baikal region (southeast Siberia), between June 2011 and April 2017. This is the first high-resolution dataset of stable isotopes of precipitation from this poorly studied region of continental Asia, which has a high potential for isotope-based palaeoclimate research. The dataset revealed distinct seasonal variations: relatively high δ¹⁸O (up to −4‰) and δD (up to −40‰) values characterize summer air masses, and lighter isotope composition (−41‰ for δ¹⁸O and −322‰ for δD) is characteristic of winter precipitation. Our results show that air temperature mainly affects the isotope composition of precipitation, and no significant correlations were obtained for precipitation amount and relative humidity. A new temperature dependence was established for weighted mean monthly precipitation: +0.50‰/°C (r² = 0.83; p <.01; n = 55) for δ¹⁸O and +3.8‰/°C (r² = 0.83, p < 0.01; n = 55) for δD. Secondary fractionation processes (e.g., contribution of recycled moisture) were identified mainly in summer from low d excess. Backward trajectories assessed with the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model indicate that precipitation with the lowest mean δ¹⁸O and δD values reaches Irkutsk in winter related to moisture transport from the Arctic. Precipitation originating from the west/southwest with the heaviest mean isotope composition reaches Irkutsk in summer, thus representing moisture transport across Eurasia. Generally, moisture transport from the west, that is, the Atlantic Ocean predominates throughout the year. A comparison of our new isotope dataset with simulation results using the European Centre/Hamburg version 5 (ECHAM5)-wiso climate model reveals a good agreement of variations in δ¹⁸O (r² = 0.87; p <.01; n = 55) and air temperature (r² = 0.99; p <.01; n = 71). However, the ECHAM5-wiso model fails to capture observed variations in d excess (r² = 0.14; p < 0.01; n = 55). This disagreement can be partly explained by a model deficit of capturing regional hydrological processes associated with secondary moisture supply in summer.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Massive barite deposits and carbonate mineralization in the Derugin Basin, Sea of Okhotsk: precipitation processes at cold seep sites

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (∼1%) in the barite fabric imply the presence of H₂S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative δ¹³C values of these carbonates (>−43.5‰ PDB) indicate methane as major carbon source; δ¹⁸O values between 4.04 and 5.88‰ PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with ¹⁴C-ages ranging from 20?680 to >49?080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO₄^2- concentrations and a parallel increase of H₂S with depth. Additionally, S and O isotope data of barite sulfate (δ³⁴S: 21.0-38.6‰ CDT; δ¹⁸O: 9.0-17.6‰ SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with ‘normal’ seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49?000 yr.     

18O/16O studies of fossil fissure fumaroles from the Valley of Ten Thousand Smokes, Alaska

At three sample sites where there are good exposures of the upper 15 m of the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS), Alaska, ¹⁸O/¹⁶O studies indicate that fumarolic activity produced a very wide range of δ¹⁸O values (?0.1 to +12.6; n=32) in the groundmass adjacent to fossil fissure fumaroles. This contrasts sharply with the uniformity of δ¹⁸O in the groundmass away from fumarolic conduits (δ¹⁸O=+5.9 to +7.1; n=7) and in all of the feldspar phenocrysts (δ¹⁸O=+6.11 to +7.5 1 for 11 samples from this study and Hildreth 1987), independent of whether these were collected from fossil fumaroles or from unaltered tuff. Only one sample contained feldspars that were even slightly ¹⁸O-enriched relative to the others (cloudy plagioclase δ¹⁸O=+8.45). and this sample also contained the most ¹⁸0-enriched groundmass of any of those analyzed (δ¹⁸O=+12.6). This preservation of primary magmatic δ¹⁸O values in the VTTS feldspar phenocrysts is clearly a consequence of the extremely short time span (i.e., 1912 to ≈1923) of vigorous, high-temperature, fumarolic activity in the 1912 ash-flow sheet. These ¹⁸O/^l6O systematica are strikingly similar to those discovered in the 2.8-Ma intracaldera Chegem Tuff (Gazis et al. 1996) and in the fossil fumaroles in the outflow sheet of the 0.76 Ma Bishop Tuff (Holt and Taylor 1998), thus confirming that a similar type of fumarolic meteoric-hydro-thermal activity occurred above the zone of intense welding in all three of these ash-flow tuffs. This is particularly important, because it provides a direct linkage between the older tuffs and the actual observations at the VTTS of steam chemistry, water/rock interaction, circulation geometry, flow velocities, and fumarolic temperatures (up to 645°C). The ¹⁸O/^l6O effects in the VTTS can all be explained in terms of a two-stage history: (a) an early, 10- to 15-year-long, high-temperature (τ;450°C), fumarolic ¹⁸O-depletion event (groundmass δ¹⁸O=?0.1 to +4.8); and (b) a subsequent, much longer-lived, low-temperature (<150°C), ¹⁸O-enrichment episode (groundmass as high as δ¹⁸O=+12.6). Steam in these low-temperature fumaroles probably passed through various parts of the same hydrothermal system associated with the earlier, higher-temperature, fumarolic activity, and a weakened form of this low-temperature hydrothermal circulation continues to the present day (Keith et al. 1992; Lowell and Keith 1991). This low-temperature ¹⁸O/¹⁶O exchange probably occurred in combination with mineralogical alteration of both the groundmass and the calcium-rich portions of feldspar phenocrysts during the waning (<150°C) stages of fumarolic activity (Spilde et al. 1993). The slight ¹⁸O enrichment of apparently pristine, transparent feldspar phenocrysts (δ¹⁸O=+7.51) in one of the ¹⁸O-depleted, meteoric-hydrothermally altered fumarolic samples (whole-rock δ¹⁸O=+4.8) probably indicates that this sample was incipiently altered at low temperatures as fumarolic activity waned, and thus may have had a whole-rock δ¹⁸O value much lower than +4.87‰ prior to 1923.     

History of anthropogenic nitrogen input to the German Bight/SE North Sea as reflected by nitrogen isotopes in surface sediments,sediment cores and hindcast models

The German Bight/SE North Sea is considered a hot-spot of river-induced eutrophication, but the scarce observational data of river nitrate loads prior to the 1970s complicate the assessment of target conditions for environmental management and legislation. Stable nitrogen isotope ratios (δ¹⁵N) in sediment records can be used to decipher historical river nitrate contributions. To better constrain pre-1970s conditions, we determined δ¹⁵N in archive sediment samples (1950–1969) and dated cores from the Helgoland depositional area. We also modeled the δ¹⁵N in past situations (1960 and 1860) using an N-isotope-tracking ecosystem model. The modeled spatial distribution of δ¹⁵N in sediments for 1960 conditions and the observed spatial pattern of δ¹⁵N in archive sediment samples (1950–1969) represent a period of moderate eutrophication. The modeled spatial distribution of δ¹⁵N in sediments for 1860 conditions (pre-industrial) showed a moderate δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N<4‰) to the open sea (δ¹⁵N∼5‰). This pattern contrasts with the δ¹⁵N pattern in modern surface sediments, which exhibits a steep and inverted δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N>9‰) to the open sea (δ¹⁵N<7‰). Modeled δ¹⁵N for 1860 conditions are consistent with δ¹⁵N values observed in dated sediment cores that span the last 900 years. Value of δ¹⁵N in sediment cores increased from approximately 1860 to 2000 by 2.5‰. The increasing trend reflects changes in the abundance and isotopic composition of riverine nitrate loads caused by anthropogenic activities. Sensitivity tests suggest that loads and isotopic ratios of nitrogen forms other than nitrate (ammonium and organic nitrogen) have minor impact on the modeled surface sediments, despite their higher abundance in the riverborne loads in the past. Our results suggest that eutrophication of the German Bight predates the 1960 period of documented rapidly increasing river loads. Pre-industrial levels of δ¹⁵N modeled with 28% of the modern annual (1990–1999) atmospheric loads and 10% of the modern annual river loads agree best with levels of δ¹⁵N (∼6‰) observed in sediments of the cores dated to 1860.     

Oxygen and hydrogen isotopes in the volcano-sedimentary complex of Huelva (Iberian Pyrite Belt): example of water circulation through a volcano-sedimentary sequence

The minerals of basic and acidic rocks from the volcano-sedimentary sequence in the Huelva area, Spain, Iberian Pyrite Belt, display an extendedδ¹⁸O enrichment. Quartzδ¹⁸O values from quartz-keratophyres vary from +10.5 to +17.0 and feldsparδ¹⁸O values from +14.4 to +16.0. For the spilite or spilitized doleritesδ¹⁸O values vary from +9.9 to +13.4 for feldspar, from +6.4 to +9.8 for chlorite, from +3.7 to +4.3 for ilmenite and from +13.6 to +14.0 for quartz, but pyroxene exhibits magmatic values, from +5.3 to +6.1 with an exception at +7.5. The chloriteδD values vary from −34 to −43‰.This is attributed to hydrothermal alteration with seawater enriched inδ¹⁸O by circulation through sediments.The temperatures of interaction determined from isotopic fractionations between minerals range from 400° to 520°C.CalculatedδD andδ¹⁸O values for water in equilibrium with the minerals at isotopic temperatures range from −16 to +5 and from +8.3 to +12.8, respectively.A model of circulation of seawater through a pile of sedimentary rocks and then through basaltic rocks is proposed to explain the high¹⁸O compositions of the rocks from the Huelva District. Water/rock mass ratios calculated from this model range between 0.3 and 0.7 for the determined range of temperatures.     

Extreme short‐term stable isotope variability revealed by continuous rainwater analysis

The continuous real‐time analysis, at 30‐s intervals, of precipitation at an Australian tropical location revealed extreme and rapidly changing δ¹⁸O and δD values related to variations in moisture source areas, transport paths and precipitation histories. The range of δ¹⁸O (?19.6‰ to +2.6‰) and δD (?140‰ to +13‰) values from 5948 measurements of nine rain events over 15 days during an 8‐month period at a single location was comparable with the range measured in 1532 monthly samples from all seven Australian Global Network of Isotopes in Precipitation stations from 1962 to 2002. Extreme variations in δ¹⁸O (?8.7‰ to ?19.6‰) and δD (?54‰ to ?140‰) were recorded within a single 4‐h period. Real‐time stable isotope monitoring of precipitation at a high temporal resolution enables new and powerful tracer applications in climatology, hydrology, ecophysiology and palaeoclimatology. Copyright © 2012 John Wiley & Sons, Ltd.