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.     

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.     

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.     

Paleoclimatic implications of the spatial patterns of modern and LGM European land-snail shell δO

The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ¹⁸O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ¹⁸O between sites but not among genera at a single location. Therefore, we group δ¹⁸O values from different genera together to map the spatial distribution of δ¹⁸O in shell carbonate. Shell δ¹⁸O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ¹⁸O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ¹⁸O data show a different gradient with δ¹⁸O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ¹⁸O values decreasing northward.     

Origin and migration of brines from Paleozoic strata in Central Tarim,China: constraints from 87Sr/86Sr, δD, δ18O and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, and δ¹⁸O of oilfield waters, and ⁸⁷Sr/⁸⁶Sr of whole rock were measured from Paleozoic strata in the Central Tarim basin, NW China. The aim is to elucidate the origin and migration of formation water and its relation to petroleum migration. High salinity oilfield waters in Carboniferous, Silurian and Ordovician reservoirs have maintained the same Na/Cl ratio as seawater, indicative of subaerially evaporated seawater. Two possible sources of evaporitic water are Carboniferous (C_II) and Cambrian, both of which contain evaporitic sediments. Geographic and stratigraphic trends in water chemistry suggest that most of the high salinity water is from the Cambrian. Strontium, H and O isotopes as well as ion chemistry indicate at least 3 end member waters in the basin. High-salinity Cambrian evaporitic water was expelled upward into Ordovician, Silurian and Carboniferous reservoirs along faults and fractures during compaction and burial. Meteoric water has likely invaded the section throughout its history as uplift created subaerial unconformities. Meteoric water certainly infiltrated Silurian and older strata during development of the C_III unconformity and again in recent times. Modern meteoric water enters Carboniferous strata from the west and flows eastward, mixing with the high salinity Cambrian water and to a lesser degree with paleometeoric water. The third end member is highly radiogenic, shale-derived water which has migrated eastward from the Awati Depression to the west. Enrichment of Ca and Sr and depletion of K, Mg, and SO₄ relative to the seawater evaporation trajectory suggest waters were affected by albitization of feldspars, dolomitization, illitization of smectite, and SO₄ reduction. The mixing of meteoric water occurred subsequently to seawater evaporation, main water-rock interactions, and brine migration. The direction of brine migration is consistent with that of petroleum migration, suggesting water and petroleum have followed the same migration pathways.     

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.     

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.

     

Chemistry,isotope values (δD, δ18O, δ34SSO4) and temperatures of the water inflows in two Gotthard tunnels,Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO₃ and Na–Ca–HCO₃ waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO₃ to Na–SO₄ waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO₄ composition. Calcium-Na–SO₄ waters are also present. They can be produced through interaction of either Na–HCO₃ waters with anhydrite or Ca–SO₄ waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO₃ waters are generated through interaction of Ca–HCO₃ waters with a local gneissic rock. The two main SO₄-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ³⁴S_SO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ³⁴S_SO4 >∼+9‰ are controlled either by bacterial SO₄ reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.     

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.     

Ground ice recharge via brine transport in frozen soils of Victoria Valley, Antarctica: Insights from modeling δO and δD profiles

Soils in the McMurdo Dry Valleys, Antarctica contain ice and considerable amounts of salt. Ice often occurs at shallow depth throughout the Dry Valleys and other areas of hyperarid permafrost, notably on Mars. This common occurrence of shallow ice is enigmatic; however, since according to published sublimation models it should disappear relatively quickly (at rates of order 0.1 mm a⁻¹) due to vapor loss to the atmosphere. This loss may be offset by recharge from snowmelt infiltrating and freezing in the soil. Herein, we present a first quantitative estimate of this recharge based on measured vertical profiles of δD and δ¹⁸O that reveal considerable detail about the sources and sinks of ice. We model these profiles, taking into account the salt content and a soil temperature record along a 1.6 m depth profile of ∼10 ka old ice-cemented soils in Victoria Valley, Antarctica. The stable isotopes of ice are enriched in heavy isotopes at the top of the ice cement (20 cm depth); both δD and δ¹⁸O values plotted against depth exhibit a concave upward curve. At depth, the isotope composition is similar to that of Lake Victoria and modern meteoric water. The concave shape of the isotope profile is suggestive of downward advection-dispersion of snowmelt water enriched in heavy isotopes into the ice cement. Our advection-dispersion model, coupled with field data, enables us to quantify the advective flux and dispersion of melt water into the ice. The advective velocity and dispersion coefficient depend on the time since advection began and the ice-to-brine ratio; they are, respectively, of the order of 10⁻¹¹-10⁻¹⁰ m s⁻¹ and 10⁻¹²-10⁻¹¹ m² s⁻¹. These values suggest that over the ∼10 ka time period, a total of 190 mm water infiltrated into the ice-cemented ground. The isotope composition and deuterium excess values of the uppermost ice cement can be modeled from snowmelt water enriched in salts using open system-Rayleigh fractionation. To develop the isotopic signature of the upper ice cement requires evaporation of ∼95% of the snowmelt water. Based on 190 mm brine infiltrating into the soil requires an initial total of ∼4 m of snowmelt water. This corresponds to ∼0.4 mm a⁻¹ suggesting that, under the current climate condition, water from snowmelt is sufficient to compensate modeled sublimation rates, and therefore conserve ground ice in Victoria Valley.     

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.     

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 -     

The δ18O and δ13C records in an aragonite stalagmite from Furong Cave,Chongqing, China: A-2000-year record of monsoonal climate

A 7-cm long aragonite stalagmite, FR0510-1, from Furong Cave, Chongqing, was dated by ²¹⁰Pb and ²³⁰Th methods, revealing a-2000-year record of climate history under the influence of the East Asian Monsoon. The FR0510-1 record resembles Dongge Cave DA record on 10–100-year scales, but quite different from the Wanxiang Cave WX42B record, indicating that while stalagmite δ¹⁸O record represents local/regional moisture change, spatial variability of the monsoonal rainfall over eastern China must take into account. During the past 2000 years, climate in Chongqing was relatively wet in the intervals of 50 BC–AD 250, AD 1150–1450 and AD 1600–1950, and relatively dry during the periods of AD 250–1150 and AD 1450–1600. Dry conditions were prevailing over the Medieval Warm Period, whereas wet climates were dominant during the most time of the Little Ice Age in Chongqing area.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Reconstructing seawater δO from paired coral δO and Sr/Ca ratios: Methods, error analysis and problems, with examples from Tahiti (French Polynesia) and Timor (Indonesia)

We compare several statistical routines that may be used to calculate δ¹⁸O_sw and SSS from paired coral Sr/Ca and δ¹⁸O measurements. Typically, the δ¹⁸O_coral-SST relationship is estimated by linear regression of coral δ¹⁸O vs. SST. If this method is applied, evidence should be given that at a particular site SST and SSS do not co-vary. In the tropical oceans, SST and δ¹⁸O_sw (SSS) often co-vary, and this will bias the estimate of the regression slope of δ¹⁸O_coral-SST. Using a stochastic model, we show that covariance leads to a bias in the coefficients of the univariate regression equations. As the slope of the δ¹⁸O_coral-SST relationship has known, we propose to insert this value for γ₁ in the regression models. This requires that the constants of the regression equations are removed. To omit the constants, we propose to center the regression equations (i.e., to remove the mean values from the variables). The statistical error propagation is calculated to assess our ability to resolve past variations in δ¹⁸O_sw (SSS). At Tahiti, we find that the combined analytical uncertainties of coral δ¹⁸O and Sr/Ca equal the amplitude of the seasonal cycle of δ¹⁸O_sw (SSS). Therefore, we cannot resolve the seasonal cycle of SSS at Tahiti. At Timor, the error of reconstructed δ¹⁸O_sw (SSS) is lower than the magnitude of seasonal variations of δ¹⁸O_sw (SSS), and the seasonal cycle of δ¹⁸O_sw (SSS) can be resolved.     

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C₃₀ diahopane/C₂₉Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C₁₉-tricyclic and C₂₄-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ¹³C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C₂₃-tricyclic/C₃₀ hopane, C₂₈-tricyclic/C₃₀ hopane, total tricyclic terpanes/hopanes and C₃₁(R + S)/C₃₀ hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C₄₁₊) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C₁₇, Ph/n-C₁₈ and low API gravities.     

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.