Depositional and diagenetic history of limestones and dolostones of the Oligo‐Miocene Kujung Formation in the Northeast Java Basin,Indonesia

Lithological and geochemical features of platformal carbonates record the signatures of the global climates and the regional environmental settings and also reconstruct the diagenetic history and porosity evolution, which are essential to evaluate the potential of hydrocarbon reservoirs. This study investigates the platformal carbonates of the Oligo‐Miocene Krunji Formation of North East Java Basin, which are potentially significant hydrocarbon reservoirs. The carbonate sequence in a 283 m thick section at Kranji in East Java is subdivided into three lithological units: limestone unit 1, dolostone unit 2, and limestone unit 3, in ascending order. The strontium‐isotope ratios of well‐preserved calcite samples indicate the depositional period from Chattian (late Oligocene) to Burdigalian (early Miocene), which is consistent with ages of the foraminifer assemblages. Unit 1 consists of low‐porosity limestone, in which two horizons of subaerial exposure are recognized by the occurrence of red‐colored matrix and lower δ¹³C values. Unit 2 consists of dolomitic rock and exhibits coarse‐grained calcitic grains and cross‐stratified structure. Considering that this unit has been subject to dolomitization, the sediment of unit 2 was initially permeable and was likely deposited in a shoal setting. The overlying unit 3 of Aquitanian–Burdigalian age is characterized by a highly granular texture. High porosity and uniformly low δ¹³C and δ¹⁸O values indicate that Unit 3 was subjected to more intense meteoric diagenesis than the Chattian unit 1. This was likely a consequence of the Antarctic ice‐sheet expansion during the Oligocene/Miocene transition, which amplified sea level change. The unit 2 dolomite has high δ¹³C and δ¹⁸O values and a high ⁸⁷Sr/⁸⁶Sr ratio which resulted from the reflux of seawater into permeable the sediment body in middle‐late Miocene (Burdigalian Tortonian) following the deposition of unit 3. The porosity and permeability of the Kujung Formation were initially controlled by sedimentological processes, but largely modified by later diagenetic processes.     

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.     

Evidence for a hypogene paleohydrogeological event at the prospective nuclear waste disposal site Yucca Mountain,Nevada, USA,revealed by the isotope composition of fluid-inclusion water

Secondary calcite residing in open cavities in the unsaturated zone of Yucca Mountain has long been interpreted as the result of downward infiltration of meteoric water through open fractures. In order to obtain information on the isotopic composition (δD and δ¹⁸O) of the mineral-forming water we studied fluid inclusions from this calcite. Water was extracted from inclusions by heated crushing and the δD values were measured using a continuous-flow isotope-ratio mass spectrometry method. The δ¹⁸O values were calculated from the δ¹⁸O values of the host calcite assuming isotopic equilibrium at the temperature of formation determined by fluid-inclusion microthermometry.The δD values measured in all samples range between ? 110 and ? 90‰, similar to Holocene meteoric water. Coupled δ¹⁸O–δD values plot significantly, 2 to 8‰, to the right of the meteoric water line. Among the various processes operating at the topographic surface and/or in the unsaturated zone only two processes, evaporation and water–rock exchange, could alter the isotope composition of percolating water. Our analysis indicates, however, that none of these processes could produce the observed large positive δ¹⁸O-shifts. The latter require isotopic interaction between mineral-forming fluid and host rock at elevated temperature (>100 °C), which is only possible in the deep-seated hydrothermal environment. The stable isotope data are difficult to reconcile with a meteoric origin of the water from which the secondary minerals at Yucca Mountain precipitated; instead they point to the deep-seated provenance of the mineral-forming waters and their introduction into the unsaturated zone from below, i.e. a hypogene origin.     

Vapour source and spatiotemporal variation of precipitation isotopes in Southwest Spain

The δ²H and δ¹⁸O composition of 77 precipitation samples collected between January 2014 and April 2019 from two sites across the Guadalquivir Basin, SW Spain, were analysed. The first site is located in an urban area of Seville at 100 km distance to the Atlantic coast and the second site is located in a dune area of the Doñana National Park a few kilometres from the coast. Sampling was performed within intervals of at least 14 days if rain occurred but frequently intervals were longer according to the rainfall incidence. Samples from both sites are available for the period February 2016 to June 2018 with six samples containing identical rain events at both locations. Precipitation weighted averages and local meteoric water lines produced by weighting and non-weighting regression methods are presented for its use in hydrological applications. Results show a remarkably high variability in δ²H and δ¹⁸O values and precipitation weighted average d-excess values of 11.8‰ and 13‰ at the sites Plaza de España and Doñana, respectively. Temperature and amount effects were found to be weak. A significant influence of secondary evaporation for single rainfall events during summer was identified by enriched isotopic signatures with reduced d-excess values plotting close or below the global meteoric water line. Backward trajectory analysis of 115 days with daily rainfall above 3 mm yield a predominant Atlantic Ocean vapour source with negligible Mediterranean influence and therefore, d-excess variability is attributed to the different ocean surface conditions of relative humidity and sea surface temperature. Parallel sampling indicate very similar isotopic signatures at both sites and point to the existence of thermal effects of the Plaza de España site in Seville city during the summer season.     

Groundwater Origin in Qanats,Chemo-Isotopic,and Hydrogeological Evidence

A systematic study of the chemo-isotopic characteristics and origin of the groundwater was carried out at six major qanats in the hyper-arid Gonabad area, eastern Iran. These qanats as a sustainable groundwater extraction technology have a long history, supporting human life for more than a thousand years in this region. The Gonabad qanats are characterized by outlet electrical conductivity (EC) values of 750 to 3900 µS/cm and HCO₃-Na-Mg and Cl-Na water types. The Gonabad meteoric water line (G_nMWL) was drawn at the local scale as δ²H = 6.32×δ¹⁸O + 8.35 (with R² = 0.90). It has a lower slope and intercept than the global meteoric water line due to different water vapor sources and isotope kinetic fractionation effects during precipitation in this arid region. The altitude effects on isotopic content of precipitation data were derived as δ¹⁸O = (−0.0031 × H_(m.a.s.l))−1.3). The δ²H and δ¹⁸O isotopes signatures demonstrate a meteoric origin of the groundwater of these qanats. The shift of the qanat's water samples from the local meteoric water line (LMWL) in a dry period with higher temperatures is most probably due to evaporation during the infiltration process and water movement in qanat gallery. Based on the isotopic results and mass balance calculations, the qanats are locally recharged from an area between 2000 to 2400 m.a.s.l of nearby carbonate formations and coarse alluvial sediments. The dissolution of evaporate interlayers in Neogene deposits deteriorates the groundwater quality, especially in Baidokht qanat.     

Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.     

Tracer-based estimation of temporal variation of water sources: an insight from supra- and subglacial environments

ABSTRACT

The temporal variations in electrical conductivity and the stable isotopes of water, δD and δ¹⁸O, were examined at Chhota Shigri Glacier, India, to understand water sources and flow paths to discharge. Discharge is highly influenced by supraglacially derived meltwater during peak ablation, and subglacial meltwaters are more prominent at the end of the melt season. The slope of the best fit linear regression line for δD versus δ¹⁸O, for both supraglacial and runoff water, is lower than that for precipitation (snow and rain) and surface ice, indicating strong isotopic fractionation associated with the melting processes. The slope of the local meteoric water line (LMWL) is close to that of the global meteoric water line (GMWL), reflecting that the moisture source is predominantly oceanic. The d-excess variation in rainwater confirms that the southwest monsoon is the main contributor during summer while the remainder including winter is mostly influenced by westerlies.     

Spatiotemporal variation of stable isotopic composition in precipitation: Post‐condensational effects in a humid area

In the present study, a 2‐year dataset on δ¹⁸O and δ²H in precipitation is used to investigate hydrometeorologic controls on the isotopic compositions in a temperate maritime climate. Data was collected in Denmark along a transect of Six sampling stations across a landscape with a small topographic gradient and predominant westerly winds. Data showed the local meteoric water line for this region is expressed by the equation δ²H = 7.4δ¹⁸O + 5.4‰. A significant trend correlating enriched isotopic values to humidities around 70% during dry season and more depleted isotopic values to humidities around 90% during wet season was derived from the dataset. Temperature was found to only influence the isotopic composition in a secondary way, whereas no significant relationship was obtained for precipitation amount and evapotranspiration. It is suggested that subcloud post‐condensation exchange strongly influences the isotopic composition at the study site. A simple model of evaporation on falling rain was applied with the aim to reproduce observational data and show the potential influence of changing humidity conditions on precipitation compositions. The rather simple model approach did not fully explain the observational data, but it highlights the drastic isotopic changes from a falling raindrop that potentially can occur due to its release into a dryer atmosphere. This study shows that regional conditions and especially humidity can alter the isotopic composition in precipitation substantially even in regions without major topographic and hydrometeorologic gradients.     

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.     

Major active faults determine the location of the Tongonan geothermal field: Evidence provided by rock alteration and stable isotope geochemistry

Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ¹⁸O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ¹⁸O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ¹⁸O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km³ reservoir, can account for the estimated 3 My age of the system.     

Isotopic composition of precipitation in a topographically steep,seasonally snow‐dominated watershed and implications of variations from the global meteoric water line

The local meteoric water line (LMWL), the functional relationship between locally measured values of δ¹⁸O and δ²H in precipitation, represents the isotopic composition of water entering hydrologic systems. The degree to which the LMWL departs from the global meteoric water line (GMWL), moreover, can reveal important information about meteoric sources of water (e.g. oceanic or terrestrial) and atmospheric conditions during transport. Here we characterize the isotopic composition of precipitation within an experimental watershed in the Western US that is subject to large topographic and seasonal gradients in precipitation. Interpreting the hydrometeorologic and spatial controls on precipitation, we constructed a seasonally weighted LMWL for southwestern Idaho that is expressed by the equation δ²H = 7.40 × δ¹⁸O ? 2.17. A seasonally weighted LMWL that is based on weighting isotopic concentrations by climatic precipitation volumes is novel, and we argue better represents the significant seasonality of precipitation in the region. The developed LMWL is considerably influenced by the semiarid climate experienced in southwest Idaho, yielding a slope and y‐intercept lower than the GMWL (δ²H = 8 × δ¹⁸O + 10). Moderate to strong correlations exist between the isotopic composition of precipitation from individual events and surface meteorologic variables, specifically surface air temperature, relative humidity, and precipitation amount. A strong negative correlation exists between the annual average isotopic composition of precipitation and elevation at individual collection sites, with a lapse rate of ?0.22‰/100 m. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Seasonal variations of deuterium and oxygen‐18 isotopes and their response to moisture source for precipitation events in the subtropical monsoon region

Deuterium and oxygen‐18 are common environmental tracers in water used to investigate hydrological processes such as evaporation and groundwater recharge, and to trace moisture source. In this study, we collected event precipitation from 01 January 2010 to 28 February 2011 at a site in Changsha, Yangtze River Basin to estimate the influence of moisture source and atmospheric conditions on stable isotope compositions. The local meteoric water line, established as δD = (8.45 ± 0.13) δ¹⁸O + (17.7 ± 0.9) (r² = 0.97, n = 189), had a higher slope and intercept than global meteoric water line. Temperature–δ¹⁸O exhibited complex correlations, with positive correlations during Nov.–Apr. superior to during Jun.–Sep., which was attributed to distinctive moisture sources, but vague the overall period; amount effect examined throughout the year. Linear regressions between δ¹⁸O and δD value in different precipitation event size classes revealed progressively decreasing slope and intercept values with decreasing precipitation amount and increasing vapour pressure deficit, indicating that small rainfall events (0–5 mm) were subject to secondary evaporation effects during rainwater descent. In contrast, snowfall and heavy precipitation events exhibited high slope and intercepts for the regression equation between δ¹⁸O and δD. High concentrations of heavy isotopes were associated with precipitation events sourced from remote westerly air masses, degenerated tropical marine air masses from the Bay of Bengal (BoB), and inland moisture in the pre‐monsoon period, as determined from backward trajectories assessed in the HYSPLIT model. Meanwhile, low concentrations of heavy isotopes were found to correspond with remote maritime moisture from BoB, the South China Sea, and the west Pacific at three different air pressures in summer monsoon and post‐monsoon using HYSPLIT and records of typhoon paths. These findings suggest that stable isotope compositions in precipitation events are closely associated with the meteorological conditions and respond sensitively to moisture source in subtropical monsoon climates. Copyright © 2013 John Wiley & Sons, Ltd.     

Composition and properties of the iron hydroxides-cemented lenses in Estonian sandstone of Middle Devonian age

The formation of hematite and goethite concretions in different sedimentary rocks including sandstones is an important diagenetic process in the geologic history of the Earth. Its interpretation can also contribute to understanding the diagenetic history of Martian iron hydroxide concretions. A case study of iron-rich concretions from Estonian Middle Devonian sandstones exposed in ancient river valleys in southeastern Estonia was carried out based on the results of mineralogical, petrographical, geochemical, petrophysical and magnetic analyses. It was found that the high Fe₂O₃(total) content (25.0–39.5%), high magnetic susceptibility, bulk and grain density, very low porosity, corrosion and fracturing of the quartz grains of the platy iron concretions are in contrast with properties of the Devonian host sandstones. However the ferrous iron content (measured as FeO) of iron-rich concretions was as low as in the other Devonian rocks, suggesting an oxidizing environment and arid climate during the cementation by iron-hydroxides. The fracturing of quartz grains cemented by iron hydroxides could take place at near-surface conditions including vadose and phreatic zones in arid climate with high evaporation rates. Such climatic conditions have been reported for the Baltic region during Devonian, Upper Permian and Triassic times. We have found that goethite is prevalent in the cement, replacing clay and carbonate minerals. We assume that this iron-rich cement is originated from the mobilization of iron in host sandstones by groundwater, associated with tectonic activity at the end of the Middle Devonian, evidenced by fracturing in Devonian outcrops and caves. Although this mobilization could occur under reducing conditions, precipitation of goethite and hematite for the cementation could take place in oxidizing environment along bedding planes close to the surface during short sedimentation breaks. Another possible time for the formation of iron concretions could be Permian, under the condition of both arid climate and tectonic activity.     

18O/16O ratios in cherts associated with the saline lake deposits of East Africa

The cherts formed from sodium silicate precursors in East African saline, alkaline lakes have δ¹⁸O values ranging from 31.1 to 44.1. The δ¹⁸O values correlate in general with lake salinities as inferred from geologic evidence, indicating that most chert was formed from its precursor in contact with lake water trapped at the time of deposition. A few of the analyzed cherts probably formed in contact with dilute meteoric water. From the widely varying δ¹⁸O values we conclude that precursors were transformed to chert in fluids of widely varying salinity and a_Na⁺/a_H⁺ ratio.     

Numerical studies of vertical Cl−, δ2H and δ18O profiles in the aquifer–aquitard system in the Pearl River Delta,China

Sedimentation may have a significant effect on the transport of solutes and environmental isotopes in sediment. The depth profiles of the Cl^?, δ²H and δ¹⁸O in a borehole in the aquifer–aquitard system in the Pearl River Delta (PRD), China, were obtained by centrifuging the core sediment samples. A one‐dimensional model based on the sedimentation and sea level changes of the PRD during the Holocene was built to investigate numerically the transport mechanisms of Cl^?, δ²H and δ¹⁸O. The sedimentation process was modelled as a moving boundary problem with the moving rate equal to the sedimentation rate. The model was calibrated and the parameters were obtained by comparing simulated and measured data. Very good agreement between all the three observed profiles and the simulated ones demonstrates the reliability of the model and the parameters. Simulation results show that the shapes of the curves are controlled by the combination of sedimentation and upper boundary conditions. Diffusion solely is adequate to reconstruct the observed profiles, which indicates that diffusion is the dominant vertical transport mechanism. The effective diffusion coefficients of the aquitard and the aquifer equal to 5.0 × 10^?11 and 2.0 × 10^?10 m²/s, respectively. The results of this study will help in understanding the transport mechanisms of solutes and environmental tracers in deltas with geology and hydrogeology similar to the PRD. Copyright © 2015 John Wiley & Sons, Ltd.     

The sulfur isotopic composition of Neoproterozoic seawater sulfate: implications for a snowball Earth?

The present study employs a method for analysis of the sulfur isotopic composition of trace sulfate extracted from carbonates collected in Namibia in order to document secular variations in the sulfur isotopic composition of Neoproterozoic oceanic sulfate and to assess variations in the sulfur cycle that may have accompanied profound climatic events that have been described as the snowball Earth hypothesis. The carbonates in the Otavi Group of Northwest Namibia contain 3-295 ppm sulfate. Positive excursions, to a high of 40‰ (CDT), occur above the lower (Chuos Formation) and upper (Ghaub Formation) glacial intervals in the Rasthof and Maieberg cap carbonates, respectively. Positive excursions at the top of the Rasthof Formation (reaching 51‰) and within the overlying Gruis Formation (34‰) do not appear to correspond to glaciation. The δ³⁴S_sulfate values within the Ombaatjie Formation exhibit shifts over relatively short stratigraphic intervals (tens of meters), varying between ∼15 and 25‰. Cap carbonates from Australia exhibit positive δ³⁴S_pyrite trends with amplitudes similar to those of Namibian δ³⁴S_sulfate, although, more data are necessary to firmly establish these δ³⁴S trends as global in nature. δ³⁴S_sulfate excursions found in Namibian cap carbonates are consistent with the snowball Earth hypothesis in that they appear to reflect nearly complete reduction of sulfate in an isolated, anoxic global ocean, although, there are other mechanisms that may have facilitated these large shifts in δ³⁴S_sulfate. Regardless, the low sulfate concentrations in Otavi carbonates, the high amplitude variability of the δ³⁴S_sulfate curve, and the apparently full reduction of sulfate (as implied from δ³⁴S_pyrite data), even in strata low in C_org, suggest that Neoproterozoic oceanic sulfate concentrations were much lower than modern values. Additionally, the buildup of ferrous iron and banded-iron formations during the Sturtian glacial event would indicate that Fe supply exceeded sulfide availability during the glacials and/or that all sulfide was fixed and buried. This could be construed as further evidence in support of low oceanic sulfate (and sulfide) at this time.     

Distribution of tritium and stable isotopes in precipitation in Syria

Abstract

The paper discusses aspects of the isotopic composition (tritium and stable isotopes) of precipitation, which was monitored from 2000 to 2003 at 12 stations in Syria. The seasonal variations in δ¹⁸O are smaller at the western stations than at the eastern ones due to low seasonal temperature variations. A good correlation between δ²H and δ¹⁸O was obtained for each station, and the slopes of the local meteoric water lines are significantly lower than the Global Meteoric Water Line. Values of d-excess decrease from 19‰ at the western stations to 13‰ at the eastern ones, indicating the influence of precipitation generated by air masses coming from the Mediterranean Sea. A reliable altitude effect represented by depletion of heavy stable isotopes (δ¹⁸O and δ²H), of about??0.21‰ and??1.47‰ per 100 m elevation, respectively, was observed. Monthly tritium contents in precipitation, and seasonal variations, are less at the western stations than at the eastern ones. The weighted mean tritium values are between 3 and 9 TU, and increase with distance from the Syrian coast by 1 TU/100 km.

Citation Al Charideh, A. R. & Abou Zakhem, B. (2010) Distribution of tritium and stable isotopes in precipitation in Syria. Hydrol. Sci. J. 55(5), 832–843.     

Oxygen and hydrogen isotope studies of plutonic granitic rocks

The primary δD values of the biotites and hornblendes in granitic batholiths are remarkably constant at about ?50 to ?85, identical to the values in regional metamorphic rocks, marine sediments and greenstones, and most weathering products in temperate climates. Therefore the primary water in these igneous rocks is probably not “juvenile”, but is ultimately derived by dehydration and/or partial melting of the lower crust or subducted lithosphere. Most granitic rocks have δ¹⁸O = +7.0 to +10.0, probably indicating significant involvement of high-¹⁸O metasedimentary or altered volcanic rocks in the melting process; such an origin is demanded for many other granodiorites and tonalites that have δ¹⁸O = +10 to +13. Gigantic meteoric-hydrothermal convective circulation systems were established in the epizonal portions of all batholiths, locally producing very low δ¹⁸O values (particularly in feldspars) during subsolidus exchange. Some granitic plutons in such environments also were emplaced as low-¹⁸O magmas probably formed by melting or assimilation of hydrothermally altered roof rocks. However, the water/rock ratios were typically low enough that over wide areas the only evidence for meteoric water exchange in the batholiths is given by low D/H ratios (δD as low as ?180); for example, because of latitudinal isotopic variations in meteoric waters, as one moves north through the Cordilleran batholiths of western North America an increasingly higher proportion of the granitic rocks have δD values lower than ?120. The lowering of δD values commonly correlates with re-setting of K-Ar ages, and in the Idaho batholith two broad zones (10,000 km²) can be defined where δD biotite <?100 and K-Ar “ages” have all been re-set to values less than 60 m.y., suggesting that the Ar loss was caused by the meteoric-hydrothermal circulation systems. In certain Precambrian batholiths, a much different type of very low-temperature, regional alteration by surface-derived waters took place over an extended period long after emplacement, producing “brick-red” feldspars and markedly discordant Rb-Sr isochron “ages”.     

Oxygen and hydrogen isotope studies of serpentinization in the Troodos ophiolite complex,Cyprus

Oxygen and hydrogen isotopic compositions were measured on 12 serpentine and 2 actinolite samples from the Troodos ophiolite complex, Cyprus. The single analyzed antigorite(δD= ?60, δ¹⁸O= 7.1) is isotopically similar to all previously analyzed antigorites from ultramafic bodies. However, although their D/H ratios are relatively “normal”(δD= ?70to?92), the δ¹⁸O values of most of the Troodos lizardite-chrysotile serpentines (+12.6 to +14.1) are much higher than the 2.0–9.3‰ range typically found in such serpentines. Such high δ¹⁸O values have previously been found only in the serpentine-like mineraloids termed “deweylites”, which apparently formed at Earth-surface temperatures, and in a single sample from Vourinos, Greece that is in contact with high-¹⁸O limestone. The Troodos lizardite-chrysotile samplescannot have formed by reaction with heated ocean waters, but instead must have formed in contact with large amounts of some type of meteoric, metamorphic, or formation water, either (1) at very low temperatures in a near-surface environment, or (2) at about 100°C from waters that were abnormally enriched in¹⁸O(δ¹⁸O ≈ +4 to +8). The latter possibility seems most plausible inasmuch as extensive evaporites were deposited throughout the Mediterranean Sea during the late Miocene, and this would have been accompanied by strong¹⁸O enrichments of the local meteoric waters. Heated ocean waters, however, probably were responsible for the formation of the actinolitic amphiboles(δ¹⁸O= 4.6 to 5.5; δD= ?51to?46) from the gabbro and ultramafic zones in the Troodos complex. The amphiboles must have formed at considerably higher temperatures and at an earlier stage than the lizardite-chrysotile serpentinization.