Dual effects of precipitation and evaporation on lake water stable isotope composition in the monsoon region

We present the results of a 3‐year monitoring programme of the stable isotope composition of lake water and precipitation at Taozi Lake, in the East Asian monsoon region of China. Our aims were to reveal the spatiotemporal pattern of variation of stable isotopes in a small closed‐basin lake and to quantitatively determine the impacts of precipitation and evaporation on the stable isotope composition of lake water under a humid monsoon climate. In the time domain, the stable oxygen isotopic ratio of the lake water (δ¹⁸O_L) exhibited substantial seasonal and interannual variations, but the isotope variations between different precipitation events substantially exceeded seasonal and interannual variations. Compared with the stable isotopes in precipitation, δ¹⁸O_L was substantially positive and d_L was negative. In the space domains, the lake water was homogeneously mixed. Indicated by statistic analyses, precipitation plays a dominant role in dynamic of the lake stable isotope during precipitation events of relatively large magnitude, whereas the effect of evaporation is dominant during smaller precipitation events. Results advance our understanding of the stable isotope change rule in the process of lake water evaporation, and it is helpful to identify the climatic significance recorded in stable isotopic compositions of lake bottom sediments.     

Deuterium‐excess determination of evaporation to inflow ratios of an alpine lake: Implications for water balance and modeling

The numerous lakes on the Tibetan Plateau play an important role in the regional hydrological cycle and water resources, but systematic observations of the lake water balance are scarce on the Tibetan Plateau. Here, we present a detailed study on the water cycle of Cona Lake, at the headwaters of the Nujiang‐Salween River, based on 3 years (2011–2013) of observations of δ¹⁸O and δ²H, including samples from precipitation, lake water, and outlet surface water. Short‐term atmospheric water vapor was also sampled for isotope analyses. The δ²H–δ¹⁸O relationship in lake water (δ²H = 6.67δ¹⁸O ? 20.37) differed from that of local precipitation (δ²H = 8.29δ¹⁸O + 12.50), and the deuterium excess (d‐excess) in the lake water (?7.5‰) was significantly lower than in local precipitation (10.7‰), indicating an evaporative isotope enrichment in lake water. The ratio of evaporation to inflow (E /I ) of the lake water was calculated using both d‐excess and δ¹⁸O. The E /I ratios of Cona lake ranged from 0.24 to 0.27 during the 3 years. Observations of atmospheric water vapor isotopic composition (δ _A ) improved the accuracy in E /I ratio estimate over a simple precipitation equilibrium model, though a correction factor method provided nearly identical estimates of E /I ratio. The work demonstrates the feasibility of d‐excess in the study of the water cycle for lakes in other regions of the world and provides recommendations on sampling strategies for accurate calculations of E /I ratio.     

南极洲万达盐湖水中方解石饱和指数的垂直变化及其控制因素

南极洲万达盐湖为饱和方解石湖水。计算出的方解石饱和指数随水深增加而变化。在Ca²⁺及HCO₃^-活度值均一的上部氧化环境湖水中,pH及溶解氧(DO)是控制该变化的主要因素,在下部还原环境湖水中,Ca²⁺及HCO₃^-的活度对方解石的饱和指数SI的变化起主要作用。这充分揭示了湖底部近代沉积物中分布较多方解石矿物的原因。     

Paleotemperature variations at Lake Caohai,southwestern China,during the past 500 years:Evidence from combined δ~(18)O analysis of cellulose and carbonates

The oxygen isotopic values of aquatic plant cellulose and carbonates in Lake Caohai sediments were measured using a continuous flow isotopic ratio mass spectrometer(CF-IRMS).Because of predictable oxygen isotopic fractionation between cellulose and its source water,the oxygen isotopic composition of paleo-lake water has been established quantitatively.Combined oxygen isotopic values of cellulose and carbonates were used in the‘Craig’equation to determine paleotemperatures and their variation in the lake during the past 500 years.Results show that the paleotemperature trend correlates well with meteorological records from Weining.There are four notable cold intervals at Lake Caohai over the past 500 years,namely 1540–1570AD,1670–1715AD,1780–1870AD and 1900–1930AD,and the former three cold intervals have been observed in the conventional Little Ice Age(LIA).These cold periods at Lake Caohai correspond well with those recorded from tree ring,peat,and ice core data from adjacent regions,particularly temperature those inferred fromδ18O of peat cellulose from Hongyuan Southwestern China.The trend in paleotemperature variations at Lake Caohai are also consistent with both the change of Indian summer monsoon,derived fromδ18O values of a stalagmite in Dongge,and a recorded shift in solar activity.The findings of this study illustrate that coupled analysis ofδ18O values of cellulose and carbonates from lake sediments may be used as a paleotemperature proxy.These results also provide further evidence of the existence of LIA in southwestern China.     

Hydrological and isotopic characterization of river water,groundwater, and groundwater recharge in the Heihe River basin,northwestern China

We used hydrochemistry and environmental isotope data (δ¹⁸O, δD, tritium, and ¹⁴C) to investigate the characteristics of river water, groundwater, and groundwater recharge in China's Heihe River basin. The river water and groundwater could be characterized as Ca²⁺? Mg²⁺? HCO₃^?? SO₄^2? and Na⁺? Mg²⁺? SO₄^2?? Cl^? types, respectively. Hydrogeochemical modelling using PHREEQC software revealed that the main hydrogeochemical processes are dissolution (except for gypsum and anhydrite) along groundwater flow paths from the upper to middle Heihe reaches. Towards the lower reaches, dolomite and calcite tend to precipitate. The isotopic data for most of the river water and groundwater lie on the global meteoric water line (GMWL) or between the GMWL and the meteoric water line in northwestern China, indicating weak evaporation. No direct relationship existed between recharge and discharge of groundwater in the middle and lower reaches based on the isotope ratios, d‐excess, and ¹⁴C values. On the basis of tritium in precipitation and by adopting an exponential piston‐flow model, we evaluated the mean residence time of shallow groundwater with high tritium activities, which was around 50 years (a). Furthermore, based on the several popular models, it is calculated that the deep groundwaters in piedmont alluvial fan zone of the middle reaches and in southern part of the lower reaches are modern water, whereas the deep groundwaters in the edge of the middle reaches and around Juyan Lake in the lower reaches of Heihe river basin are old water. Copyright © 2010 John Wiley & Sons, Ltd.     

Diagenetic fluid evolution and water-rock interaction model of carbonate cements in sandstone: An example from the reservoir sandstone of the Fourth Member of the Xujiahe Formation of the Xiaoquan-Fenggu area,Sichuan Province,China

Carbonate cement is the most abundant cement type in the Fourth Member of the Xujiahe Formation in the Xiaoquan-Fenggu area of the West Sichuan Depression. Here we use a systematic analysis of carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and enclosure homogenization temperatures to study the precipitation mechanism, pore fluid evolution, and distribution of different types of carbonate cement in reservoir sand in the study area. Crystalline calcite has relatively heavy carbon and oxygen isotope ratios(δ13C = 2.14‰, δ18O = -5.77‰), and was precipitated early. It was precipitated directly from supersaturated alkaline fluid under normal temperature and pressure conditions. At the time of precipitation, the fluid oxygen isotope ratio was very light, mainly showing the characteristics of a mixed meteoric water-seawater fluid(δ18O = -3‰), which shows that the fluid during precipitation was influenced by both meteoric water and seawater. The calcite cement that fills in the secondary pores has relatively lighter carbon and oxygen isotope ratios(δ13C = -2.36‰, δ18O = -15.68‰). This cement was precipitated late, mainly during the Middle and Late Jurassic. An important material source for this carbonate cement was the feldspar corrosion process that involved organic matter. The Ca2+, Fe3+ and Mg2+ ions released by the clay mineral transformation process were also important source materials. Because of water-rock interactions during the burial process, the oxygen isotope ratio of the fluid significantly increased during precipitation, by about 3‰. The dolomite cements in calcarenaceous sandstone that was precipitated during the Middle Jurassic have heavier carbon and oxygen isotope ratios, which are similar to those of carbonate debris in the sandstone(δ13C = 1.93‰, δ18O = -6.11‰), demonstrating that the two are from the same source that had a heavier oxygen isotope ratio(δ18O of about 2.2‰). The differences in fluid oxygen isotope ratios during cement precipitation reflect the influences of different water-rock interaction systems or different water-rock interaction strengths. This is the main reason why the sandstone containing many rigid particles(lithic quartz sandstone) has a relatively negative carbon isotope ratio and why the precipitation fluid in calcarenaceous sandstone has a relatively heavier oxygen isotope ratio.     

Bound and mobile soil water isotope ratios are affected by soil texture and mineralogy,whereas extraction method influences their measurement

Questions persist about interpreting isotope ratios of bound and mobile soil water pools, particularly relative to clay content and extraction conditions. Interactions between pools and resulting extracted water isotope composition are presumably related to soil texture, yet few studies have manipulated the bound pool to understand its influence on soil water processes. Using a series of drying and spiking experiments, we effectively labelled bound and mobile water pools in soils with varying clay content. Soils were first vacuum dried to remove residual water, which was then replaced with heavy isotope-enriched water prior to oven drying and spiking with heavy isotope-depleted water. Water was extracted via centrifugation or cryogenic vacuum distillation (at four temperatures) and analysed for oxygen and hydrogen isotope ratios via isotope ratio mass spectrometry. Water from centrifuged samples fell along a mixing line between the two added waters but was more enriched in heavy isotopes than the depleted label, demonstrating that despite oven drying, a residual pool remains and mixes with the mobile water. Soils with higher clay + silt content appeared to have a larger bound pool. Water from vacuum distillation samples have a significant temperature effect, with high temperature extractions yielding progressively more heavy isotope-enriched values, suggesting that Rayleigh fractionation occurred at low temperatures in the vacuum line. By distinctly labelling bound and mobile soil water pools, we detected interactions between the two that were dependent on soil texture. Although neither extraction method appeared to completely extract the combined bound and mobile (total water) pool, centrifugation and high temperature cryogenic vacuum distillations were comparable for both δ²H and δ¹⁸O of soil water isotope ratios.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Oxygen and hydrogen isotope ratios in tree rings: how well do models predict observed values?

We have measured annual oxygen and hydrogen isotope ratios in the α-cellulose of the latewood of oak (Quercus robur L.) growing on well-drained ground in Norfolk, UK. We compare the observed values of isotope ratios with those calculated using equations that allow for isotopic fractionation during the transfer of oxygen and hydrogen from source water taken by the tree to cellulose laid down in the cambium. The equations constitute a model in which isotopic fractionation occurs during evaporative enrichment within the leaf and during isotopic change between carbohydrates and water in the trunk during cellulose synthesis. From the relationship between isotope ratios in precipitation and α-cellulose, we deduce that the source water used by the tree comprises a constant mixture of groundwater and precipitation, chiefly from the months of May, June and July of the growth year. By selection of isotopic fractionation factors and the degree of isotope exchange within the trunk, we are able to model the observed annual values of oxygen isotope ratios of α-cellulose to a significant level (r=0.77, P<0.01). When we apply the same model to hydrogen isotope ratios, however, we find that, although we can predict the average value over the time series, we can no longer predict the year-to-year variation. We suggest that this loss of environmental signal in the hydrogen isotopes is caused by differences in the kinetic isotope effects of the biochemical reactions involved in the fixation of hydrogen in different positions of the glucose molecule. Owing to these effects, the hydrogen isotope ratios of cellulose can vary in a way not anticipated in current models and hence may induce non-climatic ‘noise’ in the hydrogen isotope time series.     

Characterization of lake water and ground water movement in the littoral zone of Williams Lake,a closed‐basin lake in north central Minnesota

Williams Lake, Minnesota is a closed‐basin lake that is a flow‐through system with respect to ground water. Ground‐water input represents half of the annual water input and most of the chemical input to the lake. Chemical budgets indicate that the lake is a sink for calcium, yet surficial sediments contain little calcium carbonate. Sediment pore‐water samplers (peepers) were used to characterize solute fluxes at the lake‐water–ground‐water interface in the littoral zone and resolve the apparent disparity between the chemical budget and sediment data. Pore‐water depth profiles of the stable isotopes δ¹⁸O and δ²H were non‐linear where ground water seeped into the lake, with a sharp transition from lake‐water values to ground‐water values in the top 10 cm of sediment. These data indicate that advective inflow to the lake is the primary mechanism for solute flux from ground water. Linear interstitial velocities determined from δ²H profiles (316 to 528 cm/yr) were consistent with velocities determined independently from water budget data and sediment porosity (366 cm/yr). Stable isotope profiles were generally linear where water flowed out of the lake into ground water. However, calcium profiles were not linear in the same area and varied in response to input of calcium carbonate from the littoral zone and subsequent dissolution. The comparison of pore‐water calcium profiles to pore‐water stable isotope profiles indicate calcium is not conservative. Based on the previous understanding that 40–50 % of the calcium in Williams Lake is retained, the pore‐water profiles indicate aquatic plants in the littoral zone are recycling the retained portion of calcium. The difference between the pore‐water depth profiles of calcium and δ¹⁸O and δ²H demonstrate the importance of using stable isotopes to evaluate flow direction and source through the lake‐water–ground‐water interface and evaluate mechanisms controlling the chemical balance of lakes. Published in 2003 by John Wiley & Sons, Ltd.     

Lacustrine sediments and lichen transplants: two contrasting and complimentary environmental archives of natural and anthropogenic lead in the South Urals, Russia

Lead (Pb) concentrations and isotope ratios of two different geochemical archives are compared; lake sediment cores and lichens (Hypogymnia physodes, naturally growing and transplanted) from a ca. 80 km-long transect centred on the Cu smelter and former mining town of Karabash, Ural Mountains, Russia. Lead concentrations in sediment cores from 10 lakes were generally low near their base and show an abrupt increase in their upper portions interpreted to coincide with the onset of large-scale smelting operations in 1910. Lead isotope ratios derived from ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb of the bottom layers differed significantly from those of the top. The top sediments have isotope ratios that show distinct end members, one of which was the stack dust from the Karabash smelter, which is similar to the Pb derived from ores from Sibay, a major mine in the Urals. The composition of the bottom sediment layers generally fall slightly off a mixing line between the top sediments and average Earth’s upper crust. Lichens transplanted from a reference site, as well as naturally growing lichens, sampled from southwest of the smelter have isotope ratios similar to those of the stack dust. Lichens to the northeast contained Pb from the smelter, but are increasingly influenced by other sources probably leaded petrol and local soils, and a signature derived from a source enriched in ²⁰⁷Pb. Vegetables collected from local kitchen gardens contained Pb from an additional atmospheric source, possibly coal. Our work confirms that: (1) Pb isotopes in lake sediments provide a long-term record of inputs and allows the characterisation of natural and anthropogenic sources; (2) Pb isotopes in lichens provide a short-term record of local and long-range atmospheric deposition at high spatial resolution and short time scales as they replace their Pb content within a few months; (3) determination of all four stable Pb isotopes is necessary for the identification of the sources of Pb and is extremely sensitive for discerning minor source signatures, even in an area with a dominant source such as a smelter. Particularly significant for the Karabash area is that ore-smelter-derived airborne Pb is a major component in the lake sediments and lichens but its contribution reaches insignificant levels ca. 40 km from the smelter.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Determination of groundwater discharge rates and water residence time of groundwater‐fed lakes by stable isotopes of water (18O, 2H) and radon (222Rn) mass balances

Lacustrine groundwater discharge (LGD) and the related water residence time are crucial parameters for quantifying lake matter budgets and assessing its vulnerability to contaminant input. Our approach utilizes the stable isotopes of water (δ¹⁸O, δ²H) and the radioisotope radon (²²²Rn) for determining long‐term average and short‐term snapshots in LGD. We conducted isotope balances for the 0.5‐km² Lake Ammelshainer See (Germany) based on measurements of lake isotope inventories and groundwater composition accompanied by good quality and comprehensive long‐term meteorological and isotopic data (precipitation) from nearby monitoring stations. The results from the steady‐state annual isotope balances that rely on only two sampling campaigns are consistent for both δ¹⁸O and δ²H and suggested an overall long‐term average LGD rate that was used to infer the water residence time of the lake. These findings were supported by the good agreement of the simulated LGD‐driven annual cycles of δ¹⁸O and δ²H lake inventories with the observed lake isotope inventories. However, radon mass balances revealed lower values that might be the result of seasonal LGD variability. For obtaining further insights into possible seasonal variability of groundwater–lake interaction, stable water isotope and radon mass balances could be conducted more frequently (e.g., monthly) in order to use the derived groundwater discharge rates as input for time‐variant isotope balances.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Towards a high-resolution,global, deep-sea chronology for the last 750,000 years

Variations in the ratio of¹⁸O/¹⁶O as measured in shells of marine calcareous microfossils are primarily dominated by changes in global ice volume; hence these variations provide a set of global time lines in deep-sea sediments. It is likely that the timing of major changes in oxygen isotope values is strongly influenced, if not controlled, by variations in the geometry of the Earth's orbit. Since the variation of orbital parameters can be accurately calculated, the opportunity exists for transforming this orbital chronology into a geological chronology.Through careful correlation of oxygen isotope records in a set of deep-sea cores from the sub-Antarctic, South Atlantic and equatorial Pacific, we have assembled a composite isotopic section spanning the last 750,000 years with an average sedimentation rate of 2.3 cm/1000 years. A new chronology for this time period was developed by adjusting the ages of the oxygen isotope stage boundaries in this composite section so as to extend the consistent phase relationships that exist between variations in oxygen isotope ratios and changes in obliquity and precession during the last 300,000 years to the entire 750,000-year record. Previously identified difficulties in phase locking precession with the filtered isotopic signal between 365,000 and 465,000 years B.P. have been resolved with the recognition that precessional variations have an average period of 19,000 years and not 23,000 years during this interval. Since this new age model yields the best match between variations in obliquity and precession and their corresponding frequency components in the oxygen isotope record, we believe that it presents the most accurate chronology yet developed for deep-sea sediments.With this new age model providing the time control, power spectral analyses of South Atlantic and sub-Antarctic chemical and biotic indices show that there is a strong tendency for variance to be concentrated at frequencies corresponding to periods of ～ 100,000, 41,000 and 23,000 years.     

Investigating the distribution and sources of organic matter in surface sediment of Coombabah Lake (Australia) using elemental,isotopic and fatty acid biomarkers

Extensive physical and biological measurements were made of the surface sediments within the shallow, semi-urbanised Coombabah Lake in southern Moreton Bay, Australia. Sediment bulk parameters (C/N ratios, δ¹³C and δ¹⁵N) and fatty acid biomarkers were used to determine distributions and sources of organic matter in the intertidal sediments. The determination of organic matter sources within coastal and estuarine settings is important in understanding the roles of organic matter as energy and nutrient sources. Spatial variability of biomarker values within the sediments were interpreted by thematic maps employing the Krigging algorithm. Grain size analysis indicated the lake was dominated by mud (<63 μm) in the southern (landward) and sand (>63 μm) in the northern (seaward) lake regions, respectively. Surface sediment organic C and N values ranged from 0.12% to 1.76% and 0.01% to 0.12% dry weight, respectively, and C/N ratios averaged 16.3±3.19%. Sedimentary δ¹³C values ranged from −26.1‰ to −20.9‰, with an average value of −23.9±1.0‰. Sedimentary δ¹⁵N values ranged from +1.7‰ to +4.8‰, with an average value of +2.8±0.8‰. Bulk sediment parameters suggested that sedimentary organic matter is provided predominantly by allochthonous sources in the form of fringing mangroves. Thirty-nine individual fatty acids were identified using gas chromatography–mass spectrometry. The mean contributions of long chain fatty acids (LCFAs), polyunsaturated fatty acids (PUFAs), saturated fatty acids (SAFAs) and bacterial fatty acids (BAFAs) were, respectively, 13.9±11.4%, 7.6±4.1%, 53.6±8.6% and 18.2±4.6% of the identified fatty acid methyl esters (FAMEs), with BAFAs occurring in all sampled sediments. Fatty acid compositions varied throughout lake sediments, which indicated spatial differences in autochthonous and allochthonous organic matter sources, including terrestrial and planktonic (i.e. zooplankton, diatoms and other algal species) sources. The contribution of organic matter from shoreline mangroves was confirmed by the presence of LCFAs and 18:2ω6 and 18:3ω3, which are markers for mangroves in this ecosystem. BAFAs were identified in increased proportions in sediments adjacent to urban developments and dominated by mud. Grain size was identified as a dominant factor in the fatty acid compositions and contributing values to FAME pool. Spatial patterns of C/N ratios, δ¹³C and δ¹⁵N values, and fatty acid biomarker contributions illustrated that there is a greater contribution of autochthonous and labile organic matter to the sedimentary organic matter pool in the northern (marine entrance) sediments compared to the more allochthonous sourced organic matter of the southern region of the lake. This study details the distribution and sources of organic matter within Coombabah Lake and illustrates the usefulness of a multiple biomarker approach in discriminating organic matter sources within estuarine environments.     

Stable isotopes of helium, nitrogen and carbon in a coastal submarine hydrothermal system

Geothermal gases from submarine and subaerial hot springs in Ensenada, Baja California Norte, Mexico, were sampled for determination of gas chemistry and helium, nitrogen and stable carbon isotope composition. The submarine hot spring gas is primarily nitrogen (56.1% by volume) and methane (43.5% by volume), whereas nearby subaerial hot spring gases are predominantly nitrogen (95–99% by volume). The N₂/Ar ratios and σ ¹⁵N values of the subaerial hot spring gas indicate that it is atmospheric air, depleted in oxygen and enriched in helium. The submarine hot spring gas is most probably derived from marine sediments of Cretaceous age rich in organic matter. CH₄ is a major component of the gas mixture (σ ¹³C = −44.05%₀), with only minor amounts of CO₂ (σ¹³C= −10.46%₀). The σ¹⁵N of N₂ is + 0.2%₀ with a very high N₂/Ar ratio of 160. The calculated isotopic equilibra tion temperature for CH₄---CO₂ carbon exchange at depth in the Punta Banda submarine geothermal field is approximately 200°C in agreement with other geothermometry estimates. The ³He/⁴He ratios of the hot spring gases range from 0.3 to 0.6 times the atmospheric ratio, indicating that helium is predominantly derived from the radioactive decay of U and Th within the continental crust. Thus, not all submarine hydrothermal systems are effective vehicles for mantle degassing of primordial helium.     

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

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

Mining lakes as groundwater‐dominated hydrological systems: assessment of the water balance of Mining Lake Plessa 117 (Lusatia,Germany) using stable isotopes

In the present study, the stable isotopes δ¹⁸O and δ²H were used for assessment of the water balance in a heterogeneously structured catchment area in the Lusatian Lignite Mining District, in particular, for estimation of the annual groundwater inflow and outflow (I_GW and O_GW) of Mining Lake Plessa 117. The application of stable isotopes was possible since the water exchange in the catchment area had reached steady‐state conditions after the abandonment of mining activities in 1968 and the filling of the voids and aquifers by re‐rising groundwater in the years thereafter. Diverging slopes of the Evaporation Line and the Global Meteoric Water Line manifested as evaporation from the lake catchment area. The calculated isotope water balance was compared with the commonly used surface water balance, which is unable to differentiate between I_GW and O_GW, and with a local groundwater model. The groundwater model calculated an I_GW of about 811 000 m³ yr^?1 and an O_GW close to zero, whereas the isotope water balance showed fluxes of about 914 000 and 140 000 m³ yr^?1, respectively. Considering the contribution of the groundwater inflow to the total annual input into the lake (ΔI_T) and the mean residence time (τ), where the groundwater model and the isotope water balance calculated 42 and 47% for ΔI_T and 4·3 and 3·9 years for τ, respectively, it was shown that both water balance calculation methods led to comparable results despite the differences in I_GW and O_GW. Copyright © 2008 John Wiley & Sons, Ltd.     

Evolution of uranogenic and thorogenic lead, 2. Some differences in the variations of the206Pb/204Pb and208Pb/204Pb ratios

On the basis of a dynamic model of a continuous Pb isotope evolution, the variations in the isotopic ratios of uranogenic and thorogenic Pb in a number of young ore deposits, ocean sediments and volcanic rocks from mid-ocean ridges, oceanic islands, island arcs and continents are evaluated. The deviations in the Th/U ratio from its model values are calculated. A model parameterT which indicates a more ancient enrichment in U/Pb (crustal-type Pb sources) or younger enrichment in U/Pb (mantle-type Pb sources) is also calculated. The relative change in the Th/U ratio is close to 1 for mantle-type Pb sources (lowerT values) and decreases for crustal-type Pb sources (higherT values). An interpretation of these changes could be connected with the differences in the U and Th geochemical behaviours in metamorphic processes under the conditions of a deeper (mantle) or crustal source owing to the differences in their valence states. In some cases they have similar (U⁴⁺ and Th⁴⁺) migration abilities; in others (U⁶⁺ and Th⁴⁺), considerably different.