Wet-dry seasonal and spatial variations in the δC and δO values of the modern endogenic travertine at Baishuitai, Yunnan, SW China and their paleoclimatic and paleoenvironmental implications

Seasonal and spatial variations in the δ¹³C and δ¹⁸O values of the modern endogenic (thermogene) travertine deposited in a calcite-depositing canal at Baishuitai, Yunnan, SW China were examined to understand their potential for paleoclimatic and paleoenvironmental implications. The sampling sites were set in the upstream, middle reach and downstream of the canal, and the modern endogenic travertine samples were collected semimonthly to measure their δ¹³C and δ¹⁸O values. It was found that both δ¹³C and δ¹⁸O values of the endogenic travertine were low in the warm rainy season and high in the cold dry season, and correlated with each other. The low δ¹⁸O values in warm rainy season were mainly related to the higher water temperature and the lower δ¹⁸O values of rainwater, and the low δ¹³C values are caused by the dilution effect of overland flow with low δ¹³C values in the warm rainy season and the reduced CO₂-degassing of canal-water caused by the dilution effect of the overland flow. The linear negative correlation between the travertine δ¹⁸O (or δ¹³C) values and rainfall amount may be used for paleo-rainfall reconstruction if one knows the δ¹⁸O (or δ¹³C) values of the fossil endogenic travertine at Baishuitai though the reconstruction was not straightforward. It was also found that there was a progressive downstream increase of the δ¹⁸O and δ¹³C values of the travertine along the canal, the former being mainly due to the preferential evaporation of H₂¹⁶O to the atmosphere and the latter to the preferential release of ¹²CO₂ to the atmosphere during CO₂-degassing. However, the downstream increase of the travertine δ¹⁸O and δ¹³C values was less intensive in rainy season because of the reduced evaporation and CO₂-degassing during the rainy season. To conclude, the downstream travertine sites could be more favorable for the paleo-rainfall reconstruction while the upstream travertine sites are more favorable for the paleo-temperature reconstruction. So, this study demonstrates that endogenic travertine, like epigenic (meteogene) tufa, could also be a good candidate for high-resolution paleoclimatic and paleoenvironmental reconstruction.     

Continental-scale patterns in modern wood cellulose δO: Implications for interpreting paleo-wood cellulose δO

The isotopic composition of ancient wood may be a useful archive of some climatic or geochemical conditions of the past, but presently there are many uncertainties that constrain such interpretations. We sampled naturally growing, predominantly native trees in forested regions of North America and the Caribbean to evaluate the strength of the relationships among cellulose δ¹⁸O (δ¹⁸O_cel), relative humidity (RH), precipitation δ¹⁸O (δ¹⁸O_ppt), and mean annual temperature (MAT) at the continental scale, and the general range of variability in δ¹⁸O_cel associated with site hydrologic conditions and species differences. We found up to 4‰ differences among different species growing at the same site, that conifer cellulose at a site is more enriched than angiosperm cellulose by 1.5‰ (p < 0.001), and that differences in landscape position, reflecting differing access to the water table, produced differences of <1‰ in δ¹⁸O_cel. At the continental scale, δ¹⁸O_cel was strongly influenced by modeled δ¹⁸O_ppt (R² = 0.80, p < 0.001). Average summer minimum RH (RH_min) combined with δ¹⁸O_ppt explained more of the variability (R² = 0.93, p < 0.001) in δ¹⁸O_cel across North American and Caribbean forests. MAT and δ¹⁸O_cel were also strongly correlated across North America (R = 0.91 and 0.95, p < 0.001, for angiosperms and conifers, respectively). The difference between δ¹⁸O_ppt and δ¹⁸O_cel is not constant (varying from 35-44‰) and is inversely correlated with δ¹⁸O_ppt. The relationships among δ¹⁸O_ppt, RH_min, δ¹⁸O_cel, and MAT established for North America and the Caribbean applied reasonably well when δ¹⁸O_cel was used to estimate MAT and δ¹⁸O_ppt in Asia, Europe, and South America, but there were important exceptions. The most accurate predictions of MAT and δ¹⁸O_ppt from δ¹⁸O_cel require RH_min. Predictions of δ¹⁸O_ppt and MAT made from δ¹⁸O_cel alone produced errors of up to 8‰ and 16 °C, respectively.     

Paleoclimatic implications of hydrogen and oxygen isotopic compositions of Cretaceous–Tertiary kaolins in the Douala Sub-Basin,Cameroon

Increased interest in paleoenvironmental studies is a result of climatic changes occurring at present and predicted for the future. Such studies could be done using the stable isotope compositions (δ²H and δ¹⁸O) of kaolins, which provide knowledge on the paleoenvironmental conditions prevailing during the time of kaolinisation. In this study, the stable isotopic compositions of clay-size fraction of kaolins occurring in Cretaceous and Tertiary Formations of the Douala Sub-Basin in Cameroon are presented, with the aim of reconstructing the paleoenvironmental conditions of the Sub-Basin. To achieve this, the clay-size fraction (< 2 μm fraction) of 8 kaolinite-rich samples were analysed for their δ²H and δ¹⁸O compositions, and results were reported as part per mil (‰) relative to the SMOW standard. The δ¹⁸O values of kaolins found in the Cretaceous–Tertiary Formations of the Douala Sub-Basin varied between +18.2 and +21.0‰, whereas the δ²H values varied between –69 and –53‰. Nine of the eleven samples plotted on the right of the supergene–hypogene line. Five of these nine samples plotted very close to the kaolinite line, which represents the composition of kaolinite in equilibrium with meteoric water at 20 °C; suggesting a supergene weathering origin of these kaolins. The determination of the temperature of kaolinisation yielded mean formation temperatures of 22 ± 2 °C and 27 ± 6 °C for Cretaceous and Tertiary kaolins, respectively. Excluding the two samples falling in the hypogene field, averages of kaolinisation temperatures were 20 and 25 °C during the Cretaceous and Tertiary periods, respectively. These temperatures are slightly below the present mean annual temperature in Douala (27 °C), thereby suggesting that the climate was becoming warmer from the Cretaceous to the Present. Therefore, Douala had a cooler and rainy climate during the Cretaceous, and the climate is gradually becoming hotter and more humid, favouring the refinement of existing kaolins and the kaolinisation of kaolin-forming minerals in the Sub-Basin.     

Modelling of the oxygen isotope evolution of seawater: implications for the climate interpretation of the δ18O of marine sediments

It is often argued that the δ¹⁸O value of oceanic water was maintained close to 0‰ for hundreds of millions of years, as a consequence of oxygen isotope exchange between oceanic crust and seawater. However, for several decades, the interpretation of the biosedimentary oxygen isotope record has conflicted with the igneous record because, with increasing age, a general trend of decreasing δ¹⁸O values (about 6‰) is observed in most carbonates, cherts and phosphates, especially for the Paleozoic and early Mesozoic. We developed a dynamical model of seawater-crust interaction that computes the δ¹⁸O value in these two reservoirs as function of time. This model takes into account the continuous production of crust at oceanic ridges, its expansion rate, the permeability profile with space and time, the mineralogical mode of the crust, and the kinetics of oxygen isotope exchange between rock-forming minerals and seawater. The model indicates that the δ¹⁸O value of seawater may vary by ±2‰ with a time response ranging from 5 to 50 Ma for expansion rates of 1 to 10 cm.a⁻¹. The variation of ±2‰ is fixed by both integrated water-rock ratio and closure time of the seawater-crust system by sediments. Variations in the oxygen isotope ratio of seawater through time have important implications for the interpretation of the systematically low δ¹⁸O values of pre-Jurassic marine sediments. According to our model, marine paleotemperatures could be up to 10°C lower than those expected when applying the classical hypothesis of an ice-free ocean with a δ¹⁸O value of −1‰.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Palynofacies patterns of the Devonian of the Parnaíba Basin,Brazil: Paleoenvironmental implications

To help describe the paleoenvironmental interpretation of one the most extensive marine Devonian successions in Brazil, palynofacies analyses were conducted on 46 samples from the Itaim (Pragian–Givetian), Pimenteira (Givetian–Frasnian) and Cabeças (Famennian) formations of the Parnaíba Basin in north–central Brazil. For the palynofacies analyses, kerogen categories were counted and subjected to cluster analyses. Five palynofacies associations were identified for three studied sections: PseudoAOM palynofacies, which consists of amorphous organic matter (AOM), pseudoamorphous and coenobial algae Quadrisporites; Transl/Nbiostr. palynofacies, which consists of translucent non-biostructured phytoclasts (well-preserved and degraded), cuticles (well-preserved and degraded), Spongiophyton and Botryococcus; Marine microplankton palynofacies, which consists of acritarchs, prasinophytes and translucent biostructured phytoclasts; Opaque palynofacies, which consists of opaque phytoclasts (equidimensional and lath shaped); and Sporomorphs palynofacies, which consists of zoomorphs (e.g., Chitinozoa) and sporomorphs (e.g., spores). The stratigraphic distribution of the five palynofacies associations reflects a continuous terrestrial influx throughout marine succession. At the Pragian–Emsian age, the woody material of Transl/Nbioestr. palynofacies prevails, suggesting a marine depositional paleoenvironment (presence of marine palynomorphs), but under deltaic influence due to the input of terrigenous material. An increasing trend of marine elements of Marine microplankton palynofacies is recorded for the Givetian, which suggests a progressive marine influence. However, during the Frasnian, the highest abundance of marine elements was recorded (Marine microplankton palynofacies). Moreover, a bloom of Maranhites spp. and prasinophytes (e.g., Tasmanites and Cymatiosphaera) was also recorded. The abrupt increase of marine palynomorphs in the Frasnian – here termed the “Maranhites Event” – has been recorded by other authors. Finally, in the Famennian, woody material was most abundant in Transl/Nbiostr. palynofacies and Sporomorphs palynofacies, which reflects a depositional trend that is strongly controlled by fluvial input into a shallow marine environment.     

Ecological stability during the LGM and the mid-Holocene in the Alpine Steppes of Tibet?

Arid and Alpine ecosystems are known for extreme environmental changes during the Late Quaternary. We hypothesize that the world's largest Alpine arid ecosystem however, the Alpine Steppes of the Tibetan highlands, remained ecologically stable during the LGM and the mid-Holocene. This hypothesis is tested by distributional range of plant species, plant life forms and rate of endemism. The set of character species has a precipitation gradient between 50 and 350 mm/a, testifying for resilience to precipitation changes. 83% of the species have a wider vertical range than 1000 m used as a proxy for resilience to temperature changes. 30% of the species are endemic with 10 endemic genera, including plate-shaped cushions as a unique plant life form. These findings are in line with palaeo-ecological proxies (δ¹⁸O, pollen) allowing the assumption that Alpine Steppes persisted during the LGM with 3 to 4 K lower summer temperatures.During the mid-Holocene, forests could have replaced Alpine Steppes in the upper catchments of the Huang He, Yangtze, Mekong, Salween and Yarlung Zhangbo, but not in the interior basins of the north-western highlands, because the basins were then flooded, suppressing forests and supporting the environmental stability of this arid Alpine grassland biome.     

Paleo-climate of the Boise area, Idaho from the last glacial maximum to the present based on groundwater δH and δO compositions

A 30 ka paleo-climate record of the Boise area, Idaho, USA has been delineated using groundwater stable isotopic compositions. Groundwater ages are modern (cold batholith), 5-15 ka (thermal batholith) , 10-20 ka (frontal fault) , and 20-30 ka (Snake River plain thermal). The stable isotopic composition of groundwaters have been used as a surrogate for the stable isotopic composition of precipitation. Using δ²H and δ¹⁸O compositions, local groundwater lines (LGWL's) were defined for each system. Each LGWL has been evaluated with defined slopes of 6.94 and 8, respectively, and resulting deuterium excess values (d) were found for each groundwater system for each slope. Time dependent changes in moisture source humidity and temperature, and Boise area recharge temperatures, calculated from stable isotopic data and the deuterium excess factors, agree with previous paleo-climate studies. Results indicate that from the last glacial maximum to the present time the humidity over the ocean moisture source increased by 9%, sea surface temperature at the moisture source increased 6-7°C, and local Boise temperature increased by 4-5°C. A greater increase of temperature at the moisture source as compared to the Boise area may impart be due to a shift in the moisture source area.     

The record of temperature, wind velocity and air humidity in the δD and δO of water inclusions in synthetic and Messinian halites

Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L⁻¹) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ¹⁸O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s⁻¹, slopes of the δD-δ¹⁸O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ¹⁸O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ¹⁸O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.     

Isotope Characteristics (δ13C, δ18O) of Continental Carbonates from Permian‒Triassic Rocks in the Northeastern Russian Plate: Paleoclimatic and Biotic Reasons and Chemostratigraphy

Lithology and Mineral Resources - Carbon and oxygen isotope compositions were determined in the pedogenic, sedimentary, and organogenic carbonates from Upper Permian (Vyatkian Stage) and Lower...     

Identifying sources of groundwater in the lower Colorado River valley, USA, with δ18O, δD, and 3H: implications for river water accounting

Isotope measurements (¹⁸O, D, ³H) indicate groundwater origin in the Lower Colorado River Valley (LCRV) and provide an alternative, or supplement, to the US Bureau of Reclamations proposed accounting surface method. The accounting surface method uses a hydraulic criterion to identify certain wells away from the flood plain that will eventually yield mainstream Colorado River water. New isotope data for 5 surface-water and 18 groundwater sites around Topock Marsh, Arizona, are compared with river-water data (1974–2002) from 11 sites between Utah and Mexico and with groundwater data from previous LCRV studies. Three groundwater sources are repeatedly identified in the LCRV: (1) local recharge derived from precipitation, usually winter rain, plots slightly below the global meteoric water line (GMWL) and has D values that are 20 greater than those of recent river water; (2) older (pre-1950) upper basin river-water plots on or near the GMWL, distinct from local rainfall and recent river water; and (3) recent (post-1950) Colorado River water, including Topock Marsh samples, plots below the GMWL along an evaporation trend. Large floods, as in 1983, complicate interpretation by routing less evaporated upper basin water into the LCRV; however, tritium content can indicate the age of a water. River-water tritium has declined steadily from its peak of 716 TU in 1967 to about 11 TU in 2002. Mixtures of all three groundwater sources are common.

---

Resumen Mediciones isotópicas (¹⁸O, D, ³H) indican cual es el origen del agua subterránea en el Valle Bajo del Río Colorado (LCRV) y aportan una alternativa, o complemento, para el método superficie de conteo propuesto por el Buró de Reclamación de Estados Unidos. El método superficie de conteo utiliza un criterio hidráulico para identificar ciertos pozos alejados de la planicie de inundación que eventualmente producirán agua a partir de la corriente principal del Río Colorado. Los nuevos datos isotópicos para 18 sitios de agua subterránea y 5 sitios de agua superficial cerca de los Pantanos Topock, Arizona, se comparan con datos de agua de río (1974–2002) provenientes de 11 sitios localizados entre Utah y México, y con datos de aguas subterráneas de estudios previos realizados en el LCRV. Se identifican reiteradamente tres fuentes de aguas subterráneas en el LCRV: (1) recarga local derivada de precipitación, generalmente lluvia de invierno, cuya composición cae ligeramente por debajo de la línea de agua meteórica global (GMWL) y tiene valores D que son 20 mayores que los reportados para agua de río reciente; (2) el agua de río más vieja (pre-1950) de la cuenca alta cuya composición cae sobre o cerca de la GMWL, diferente de la lluvia local y del agua de río reciente; (3) agua reciente (post-1950) del Río Colorado, incluyendo muestras de los Pantanos Topock, con composición por debajo de la GMWL a lo largo de una tendencia a la evaporación. Inundaciones grandes, como en 1983, complican la interpretación al transmitir menos agua evaporada de la cuenca alta hacia el LCRV; sin embargo, el contenido de tritio puede indicar la edad del agua. El contenido de tritio en agua de río ha disminuido constantemente desde la concentración pico de 716 TU en 1967 a cerca de 11 TU en 2002. Es común que exista mezclas de las tres fuentes de agua subterránea.

---

Résumé Les mesures isotopiques (d18O, dD, 3H) indiquent les origine de leaux souterraines dans la Vallée de la Rivière du Bas Colorado (LCRV) et sont une alternative, ou un supplément, à la méthode des bilans hydrologiques proposée par du «US Bureau of Reclamation». Cette méthode de bilan hydrologique utilise un critère hydraulique permettant didentifier certains puits hors de la plaine dinondation qui pomperaient une part non négligeable de leur eau dans la rivière Colorado. De nouvelles données isotopiques provenant de 5 sites deau de surface et 18 deaux souterraines autour de Topock Marsh en Arizona, sont comparées avec les données (1974–2000) de 11 sites localisés entre Utah et Mexico, ainsi que des données dautres études sur la LCRV. Ces sources deaux souterraines sont identifiées à plusieurs reprises dans la LCRV: (1) la recharge locale dérivant des précipitations, généralement les pluies hivernales, se retrouvent légèrement sous la ligne deau météoritique globale (GMWL) et possède des valeurs de dD 20% supérieures aux valeurs des eaux récentes de la rivière; (2) les eaux vieilles (pre-1950) du bassin supérieur de la rivière possèdent une valeurs très proches de la GMWL, distinctes des valeurs de la pluie locale et des eaux récentes de la rivière; et (3) les eaux récentes (post-1950) de la Rivière Colorado, incluant les échantillons de Topock Marsh, se positionnent à côté de la GMWL sur une droite dévaporation. Les grandes inondations, par exemple celle de 1983, compliquent linterprétation en reprenant dans la LCRV moins deaux marquées comme évaporées et provenant du bassin supérieur; par ailleurs le pic de tritium est descendu de 716 TU en 1967 à 11 TU en 2002. Les mélanges de ces trois sources sont assez fréquentes.

     

Similarity between C,N and S stable isotope profiles in European spruce forest soils: implications for the use of δ34S as a tracer

Stable isotope systematics of C, N and S were studied in soils of 5 European forest ecosystems. The sites were located along a North–South transect from Sweden to Italy (mean annual temperatures from +1.0 to +8.5 °C, atmospheric deposition from 2 to 19 kg N ha⁻¹ a⁻¹, and from 6 to 42 kg S ha⁻¹ a⁻¹). In Picea stands, the behavior of C, N and S isotopes was similar in 3 aspects: (1) assimilation favored the lighter isotopes ¹²C, ¹⁴N and ³²S; (2) mineralization in the soil profile left in situ residues enriched in the heavier isotopes ¹³C, ¹⁵N and ³⁴S; and (3) NO₃–N as well as SO₄–S in soil solution was isotopically lighter compared to the same species in the atmospheric input. In this study, emphasis was placed on S isotope profiles which so far have been investigated to a much lesser extent than those of C and N. Sulfate in monthly samples of atmospheric input had systematically higher δ³⁴S ratios than total soil S at the 0–5 cm depth, on average by 4.0‰. Sulfate in the atmospheric input had higher δ³⁴S ratios than in deep (>50 cm) lysimeter water, on average by 3.2‰. Organic S constituted more than 50% of total soil S throughout most of the profiles (0–20 cm below surface). There was a tendency to isotopically heavier organic S and lighter inorganic SO₄–S, with ester SO₄–S heavier than C-bonded S at 3 of the 5 sites. With an increasing depth (0 to 20 cm below surface), δ¹³C, δ¹⁵N and δ³⁴S ratios of bulk soil increased on average by 0.9, 4.2 and 1.6‰, respectively, reflecting an increasing degree of mineralization of organic matter. The isotope effects of C, N and S mineralization were robust enough to exist at a variety of climate conditions and pollution levels. In the case of S, the difference between isotope composition of the upper organic-rich soil horizon (lower δ³⁴S) and the deeper sesquioxide-rich soil horizons (higher δ³⁴S) can be used to determine the source of SO₄ in streams draining forests. This application of δ³⁴S as a tracer of S origin was developed in the Jezeřı́ catchment, Czech Republic, a highly polluted site suffering from spruce die-back. In 1996–1997, the magnitude and δ³⁴S of atmospheric input (20 kg S ha⁻¹ a⁻¹, 5.8‰) and stream discharge (56 kg S ha⁻¹ a⁻¹, 3.5‰) was monitored. Export of S from the catchment was 3 times higher than contemporary atmospheric input. More than 50% of S in the discharge was represented by release of previously stored pollutant S from the soil. Stable isotope systematics of Jezeřı́ soil S (mean of 2.5‰ in the O+A horizon, 4.8‰ in the B horizon, and 5.8‰ in the bedrock) suggests that most of the soil-derived S in discharge must come from the isotopically light organic S present in the upper soil horizon, and that mineralized organically-cycled S is mainly flushed out during the spring snowmelt. The fact that a considerable proportion of incoming S is organically cycled should be considered when predicting the time-scale of acidification reversal in spruce die-back affected areas.     

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

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.     

Variations in δ18O, δD,and the concentration of pollen and spores in an autochthonic heterogeneous massive ice on the Erkutayaha River in the southern part of the Yamal Peninsula

Doklady Earth Sciences -     

Spatial patterns of soil δC reveal grassland-to-woodland successional processes

Many grasslands and savannas around the world have experienced woody plant encroachment in recent history. In the Rio Grande Plains of southern Texas, subtropical woodlands dominated by C₃ trees and shrubs have become significant components of landscapes once dominated almost exclusively by C₄ grasslands. In this study, spatial variation of soil δ¹³C to was used to investigate patterns of transformation. Previous research has shown that grassland-to-shrubland transitions are initiated when discrete, multi-species shrub clusters organized around a honey mesquite (Prosopis glandulosa) tree nucleus established in grassland. It is inferred from space-for-time substitution and modeling studies that as new shrub clusters are initiated and existing clusters enlarge, coalescence will occur, leading to the formation of groves; and that groves will eventually merge to form woodlands. The hypothesis that present-day mesquite groves represent areas where individual discrete shrub clusters have proliferated and coalesced was evaluated by comparing patterns of soil δ¹³C within isolated shrub clusters (n = 6) to those in nearby groves (n = 3). Mean soil δ¹³C within discrete clusters was lowest in the center (−23.3‰), increased exponentially toward the dripline (−20.1‰), and stabilized at a relatively high value approximately 15 cm beyond the dripline (−18.9‰). The spatial structure of soil δ¹³C in groves was consistent with that which would be expected to occur if present-day grove communities were a collection of what once were individual discrete clusters that had fused. As such, it provides direct evidence in support of conceptual and mathematical models derived from indirect assessments. However, spatial patterns of soil δ¹³C suggest that groves are not simply a collection of clusters with respect to primary production and SOC turnover. This study illustrates how soil δ¹³C values can be used to reconstruct successional processes accompanying vegetation compositional change, and its consequences for ecosystem function.