Holocene hydrological variability of Lake Ladoga,northwest Russia,as inferred from diatom oxygen isotopes

This article presents a new comprehensive assessment of the Holocene hydrological variability of Lake Ladoga, northwest Russia. The reconstruction is based on oxygen isotopes of lacustrine diatom silica (δ¹⁸O_diatom) preserved in sediment core Co 1309, and is complemented by a diatom assemblage analysis and a survey of modern isotope hydrology. The data indicate that Lake Ladoga has existed as a freshwater reservoir since at least 10.8 cal. ka BP. The δ¹⁸O_diatom values range from +29.8 to +35.0‰, and relatively higher δ¹⁸O_diatom values around +34.7‰ between c. 7.1 and 5.7 cal. ka BP are considered to reflect the Holocene Thermal Maximum. A continuous depletion in δ¹⁸O_diatom since c. 6.1 cal. ka BP accelerates after c. 4 cal. ka BP, indicating Middle to Late Holocene cooling that culminates during the interval 0.8–0.2 cal. ka BP, corresponding to the Little Ice Age. Lake‐level rises result in lower δ¹⁸O_diatom values, whereas lower lake levels cause higher δ¹⁸O_diatom values. The diatom isotope record gives an indication for a rather early opening of the Neva River outflow at c. 4.4–4.0 cal. ka BP. Generally, overall high δ¹⁸O_diatom values around +33.5‰ characterize a persistent evaporative lake system throughout the Holocene. As the Lake Ladoga δ¹⁸O_diatom record is roughly in line with the 60°N summer insolation, a linkage to broader‐scale climate change is likely.     

A reassessment of late glacial – Holocene diatom oxygen isotope record from Lake Baikal using a geochemical mass‐balance approach

We present a new palaeoenvironmental record of hydrological variability in Lake Baikal, based on re‐modelled δ¹⁸O_diatom values of diatom silica (δ¹⁸O_modelled), where the residual contaminants are identified and compensated for using electron optical imaging and whole‐sample geochemistry. δ¹⁸O_modelled interpretations are based on the balance between rivers with high δ¹⁸O values and rivers with low δ¹⁸O values. Isotopic variability is related to latitudinal differences in precipitation which feed these rivers. The δ¹⁸O_modelled record suggests that rather moist conditions prevailed in the Lake Baikal region during the latter stages of the Younger Dryas. Throughout the Holocene, episodes of low δ¹⁸O_modelled values are, in general, in good agreement with increases in percentage haematite‐stained grains in North Atlantic sediments (indicative of ice‐rafted debris events). Rivers with southerly catchments dominate fluvial input especially between c. 3.3 and 2 cal ka BP, concurrent with high precipitation in the Lake Baikal region. Copyright © 2011 John Wiley & Sons, Ltd.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

The effect of species on lacustrine δ18Odiatom and its implications for palaeoenvironmental reconstructions

The oxygen isotope composition of diatom silica (δ¹⁸O_diatom) is increasingly being used to reconstruct climate from marine and lacustrine sedimentary archives. Although diatoms are assumed to precipitate their frustule in isotopic equilibrium with their surrounding water, it is unclear whether internal processes of a given species affect the fractionation of oxygen between the water and the diatom. We present δ¹⁸O_diatom data from two diatom size fractions (3–38 and >38 µm) characterized by different species in a sediment core from Heart Lake, Alaska. Differences in δ¹⁸O_diatom between the two size fractions varies from 0 to 1.2‰, with a mean offset of 0.01‰ (n = 20). Fourier transform infrared spectroscopy confirms our samples consist of pure biogenic silica (SiO₂) and δ¹⁸O_diatom trends are not driven by contamination. The maximum offset is outside the range of error, but the mean is within analytical error of the technique (± 1.06‰), demonstrating no discernible species‐dependent fractionation in δ¹⁸O_diatom. We conclude that lacustrine δ¹⁸O_diatom measurements offer a reliable and valuable method for reconstructing δ¹⁸O_water. Considering the presence of small offsets in our two records, we advise interpreting shifts in δ¹⁸O_diatom only where the magnitude of change is greater than the combined analytical error.     

New insights into Holocene atmospheric circulation dynamics in central Scandinavia inferred from oxygen‐isotope records of lake‐sediment cellulose

St. Amour, N. A., Hammarlund, D., Edwards, T. W. D. & Wolfe, B. B. 2010: New insights into Holocene atmospheric circulation dynamics in central Scandinavia inferred from oxygen‐isotope records of lake‐sediment cellulose. Boreas, Vol. 39, pp. 770–782. 10.1111/j.1502‐3885.2010.00169.x. ISSN 0300‐9843 Cellulose‐inferred lakewater oxygen‐isotope records have been obtained from two hydrologically open basins (Lake Spåime and Lake Svartkälstjärn), located on a west–east transect across central Sweden, to investigate changes in atmospheric circulation patterns during the Holocene. The Lake Spåime δ¹⁸O record is sensitive to changes in the seasonal distribution of precipitation in the Scandes Mountains of west‐central Sweden, and thus generally portrays variations in δ¹⁸O of precipitation (δ¹⁸O_P) that are governed predominantly by the influence of air masses originating from the North Atlantic. In contrast, the Lake Svartkälstjärn δ¹⁸O record appears to reflect the varying influence of air masses delivering moisture from the North Atlantic and the Baltic Sea. A comparison of inferred changes in δ¹⁸O_P over the Holocene between the two sites reveals systematic patterns of variability over widely different time scales. These include: (1) a previously recognized long‐term regional decline in δ¹⁸O_P, possibly in response to the declining vigour of Northern Hemisphere atmospheric circulation related to decreasing summer solar insolation; (2) newly identified inverse centennial‐ to millennial‐scale δ¹⁸O_P fluctuations at the two sites that may be linked to changes in modes of atmospheric circulation analogous to those described at interannual to multidecadal time scales by the North Atlantic Oscillation (NAO) index; and (3) a prolonged interval of apparent climatic stability in the mid‐Holocene (c. 6300–4200 cal. yr BP) characterized by persistently negative NAO‐like circulation.     

The influence of hydrology and climate on the isotope geochemistry of playa carbonates: a study from Pilot Valley, NV, USA

Carbonates often accompany lake and lake‐margin deposits in both modern and ancient geological settings. If these carbonates are formed in standing water, their stable isotope values reflect the aquatic chemistry at the time of precipitation and may provide a proxy for determining regional hydrologic conditions. Carbonate rhizoliths and water samples were collected from a playa lake in eastern Nevada. Pilot Valley (～43°N) is a closed‐basin, remnant playa from the Quaternary desiccation of palaeo‐Lake Bonneville. Water is added to the playa margin by free convection of dense brines to the east and forced convection of freshwater off the alluvial fan to the west. Both freshwater and saline springs dot the playa margin at the base of an alluvial fan. Water samples collected from seven springs show a range from ?16 to ?0·2‰ (Vienna Standard Mean Ocean Water), and are consistent with published values. The δ¹⁸O_calcite values from rhizolith samples range from ?18·3 to ?6·7‰ (Vienna Pee Dee Belemnite), and the average is ?12‰ V‐PDB (1 ? σ SD 2‰). With the exception of samples from Little Salt Spring, the range in the δ¹⁸O_calcite values collected from the rhizoliths confirms that they form in equilibrium with ambient water conditions on the playa. The initial geochemical conditions for the spring waters are dictated by local hydrology: freshwater springs emerge in the northern part of the basin to the east of a broad alluvial fan, and more saline springs emerge to the south where the influence of the alluvial fan diminishes. Rhizoliths are only found near the southern saline springs and their δ¹³C_calcite values, along with their morphology, indicate that they only form around saltgrass (Distichlis sp.). As the residence time of water on the playa increases, evaporation, temperature change and biological processes alter the aquatic chemistry and initiate calcite precipitation around the plant stems. The range in δ¹⁸O_calcite values from each location reflects environmental controls (e.g. evaporation and temperature change). These rhizoliths faithfully record ambient aquatic conditions during formation (e.g. geochemistry and water depth), but only record a partial annual signal that is constrained by saltgrass growth and the presence of standing water on the playa margin.     

δ18O and δ13C in fossil shells of Radix sp. from the sediment succession of a dammed palaeo‐lake in the Yarlung Tsangpo valley,Tibet, China

A series of confirmed and suspected dammed palaeo‐lake sedimentary successions is scattered within the middle Yarlung Tsangpo valley in Tibet. However, the chronology, the genesis of the dam and its location, the water level of the dammed lake, the process of dam failure and the spatiotemporal relationships between the sedimentary successions remain controversial. Here, we focus on one sedimentary succession of the suspected dammed palaeo‐lake at Xigazê. We measured the grain‐size distribution, magnetic susceptibility, organic and inorganic carbon content, and δ¹³C_org and δ¹⁵N_total ratios of the sediments. In addition, we measured the δ¹⁸O_shell and δ¹³C_shell values of modern and fossil Radix sp. shells, and the δ¹⁸O_water and δ¹³C_DIC values of the ambient water with different hydrological regimes. The results indicate that the δ¹⁸O_shell values of modern Radix sp. and the δ¹⁸O_water of the ambient water body significantly depend on its hydrological status. In addition, a strong positive relationship was observed between δ¹⁸O_shell values of modern Radix sp. shells and the δ¹⁸O_water of the ambient water on the Tibetan Plateau. According to this correlation, the δ¹⁸O_water values of the palaeo‐water body are reconstructed using the δ¹⁸O_shell values of Radix sp. fossil shells in the Xigazê section. Further, based on the δ¹⁸O_shell values of fossil Radix sp., the reconstructed δ¹⁸O_water of the palaeo‐water body and the specific habitats of Radix sp., we infer that the sedimentary succession in the Xigazê broad valley was mainly formed within the backwater terminal zone of a dammed palaeo‐lake and that the elevation of the water level of the lake was approximately 3811 m a.s.l. AMS ¹⁴C dating indicates that the deposits of the dammed palaeo‐lake were formed at about 33–22 cal. ka BP. Finally, the presence of Radix sp. fossil shells within the Xigazê section suggests that Radix sp. survived the late Last Glacial Period on the Tibetan Plateau.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Multi‐basin depositional framework for moisture‐balance reconstruction during the last 1300 years at Lake Bogoria,central Kenya Rift Valley

Multi‐proxy analysis of sediment cores from five key locations in hypersaline, alkaline Lake Bogoria (central Kenya Rift Valley) has allowed reconstruction of its history of depositional and hydrological change during the past 1300 years. Analyses including organic matter and carbonate content, granulometry, mineralogical composition, charcoal counting and high‐resolution scanning of magnetic susceptibility and elemental geochemistry resulted in a detailed sedimentological and compositional characterization of lacustrine deposits in the three lake basins and on the two sills separating them. These palaeolimnological data were supplemented with information on present‐day sedimentation conditions based on seasonal sampling of settling particles and on measurement of physicochemical profiles through the water column. A new age model based on ²¹⁰Pb, ¹³⁷Cs and ¹⁴C dating captures the sediment chronology of this hydrochemically complex and geothermally fed lake. An extensive set of chronological tie points between the equivalent high‐resolution proxy time series of the five sediment sequences allowed transfer of radiometric dates between the basins, enabling interbasin comparison of sedimentation dynamics through time. The resulting reconstruction demonstrates considerable moisture‐balance variability through time, reflecting regional hydroclimate dynamics over the past 1300 years. Between ca 690 and 950 AD , the central and southern basins of Lake Bogoria were reduced to shallow and separated brine pools. In the former, occasional near‐complete desiccation triggered massive trona precipitation. Between ca 950 and 1100 AD , slightly higher water levels allowed the build‐up of high pCO ₂ leading to precipitation of nahcolite still under strongly evaporative conditions. Lake Bogoria experienced a pronounced highstand between ca 1100 and 1350 AD , only to recede again afterwards. For a substantial part of the time between ca 1350 and 1800 AD , the northern basin was probably disconnected from the united central and southern basins. Throughout the last two centuries, lake level has been relatively high compared to the rest of the past millennium. Evidence for increased terrestrial sediment supply in recent decades, due to anthropogenic soil erosion in the wider Bogoria catchment, is a reason for concern about possible adverse impacts on the unique ecosystem of Lake Bogoria.     

Holocene monsoon climate documented by oxygen and carbon isotopes from lake sediments and peat bogs in China: a review and synthesis

There has been much recent debate about Holocene climate variation in the monsoon region of China, especially the temporal pattern of variations in precipitation, the time-transgressive nature of the Holocene precipitation maximum, and the extent to which variations in regions influenced by the Indian Summer Monsoon (ISM) and the East Asian Summer Monsoon (EASM) have been synchronous. We summarize and compare carbonate oxygen-isotope records (δ¹⁸O_carb) from ten lakes within the present-day ISM region. We discuss their paleoclimate significance considering the present-day moisture source, isotopic composition of precipitation and the hydrological setting. The δ¹⁸O_carb records are controlled mainly by the isotopic composition of lake water, which in turn is a function of regional Precipitation/Evaporation (P/E) balance and the proportion of precipitation that is monsoon-derived. We normalized the δ¹⁸O_carb data and used these records to generate an integrated moisture index. This index, along with oxygen-isotope records from speleothems and carbon-isotope records (δ¹³C_org) from peats within the monsoon region, suggests that Holocene climate was broadly synchronous across the monsoon region and, within the limits of accuracy of the existing age models, provides no strong evidence for previously-proposed anti-phasing of the ISM and the EASM. Stable-isotope records from lake sediments and peat bogs have excellent potential for providing high-quality paleoclimate data for monsoon Asia, and complement high-resolution speleothem sequences, which are only found in certain localities.     

Seasonal water-column dynamics of dissolved inorganic carbon stable isotopic compositions (δCDIC) in small hardwater lakes in Minnesota and Montana

The carbon stable isotopic value of dissolved inorganic carbon (δ¹³C_DIC) was measured over several years at different depths in the water column in six carbonate-precipitating temperate lakes. δ¹³C_DIC behavior in three of these lakes departed from the conventional model wherein epilimnetic waters are seasonally enriched relative to all hypolimnetic waters, and in general δ¹³C_DIC values in the water column were not readily correlated to parameters such as lake stratification, algal productivity, hydraulic residence time, or water chemistry. Additionally, the processes implicated in generating the δ¹³C_DIC values of individual lakes differ between lakes with similar δ¹³C_DIC compositions. Each lake thus initially appears idiosyncratic, but when the effects of carbonate mineral equilibria, microbial activity, and lake residence time are viewed in terms of the magnitude of distinct DIC pools and fluxes in stratified lakes, generalizations can be made that allow lakes to be grouped by δ¹³C_DIC behavior. We recognize three modes in the relationship between δ¹³C_DIC values and DIC concentration ([DIC]) of individual lakes: (A) δ¹³C_DIC values decreasing with increasing [DIC]; (B) δ¹³C_DIC values increasing with increasing [DIC]; (C) δ¹³C_DIC values decreasing with increasing [DIC] but increasing again at the highest [DIC]. This approach is useful both in understanding δ¹³C_DIC dynamics in modern hardwater lakes and in reconstructing the environmental changes recorded by sedimentary δ¹³C components in the lacustrine paleorecord.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

Genesis of the Changba–Lijiagou Giant Pb-Zn Deposit, West Qinling, Central China: Constraints from S-Pb-C-O isotopes

The extensive Changba-Lijiagou Pb-Zn deposit is located in the north of the Xihe–Chengxian ore cluster in West Qinling. The ore bodies are mainly hosted in the marble, dolomitic marble and biotite-calcite-quartz schist of the Middle Devonian Anjiacha Formation, and are structurally controlled by the fault and anticline. The ore-forming process can be divided into three main stages, based on field geological features and mineral assemblages. The mineral assemblages of hydrothermal stage I are pale-yellow coarse grain, low Fe sphalerite, pyrite with pits, barite and biotite. The mineral assemblages of hydrothermal stage II are black-brown cryptocrystalline, high Fe shalerite, pyrite without pits, marcasite or arsenopyrite replace the pyrite with pits, K-feldspar. The features of hydrothermal stage III are calcite-quartz-sulfide vein cutting the laminated, banded ore body. Forty-two sulfur isotope analyses, twenty-five lead isotope analyses and nineteen carbon and oxygen isotope analyses were determined on sphalerite, pyrite, galena and calcite. The δ34 S values of stage I(20.3 to 29.0‰) are consistent with the δ34 S of sulfate(barite) in the stratum. Combined with geological feature, inclusion characteristics and EPMA data, we propose that TSR has played a key role in the formation of the sulfides in stage I. The δ34 S values of stage II sphalerite and pyrite(15.1 to 23.0‰) are between sulfides in the host rock, magmatic sulfur and the sulfate(barite) in the stratum. This result suggests that multiple S reservoirs were the sources for S2-in stage II. The δ34 S values of stage III(13.1 to 22‰) combined with the structure of the geological and mineral features suggest a magmatic hydrothermal origin of the mineralization. The lead isotope compositions of the sulfides have 206 Pb/204 Pb ranging from 17.9480 to 17.9782, 207 Pb/204 Pb ranging from 15.611 to 15.622, and 208 Pb/204 Pb ranging from 38.1368 to 38.1691 in the three ore-forming stages. The narrow and symmetric distributions of the lead isotope values reflect homogenization of granite and mantle sources before the Pb-Zn mineralization. The δ13 CPDB and δ18 OSMOW values of stage I range from-0.1 to 2.4‰ and from 18.8 to 21.7‰. The values and inclusion data indicate that the source of fluids in stage I was the dissolution of marine carbonate. The δ13 CPDB and δ18 OSMOW values of stage II range from-4 to 1‰ and from 12.3 to 20.3‰, suggesting multiple C-O reservoirs in the Changba deposit and the addition of mantle-source fluid to the system. The values in stage III are-3.1‰ and 19.7‰, respectively. We infer that the process of mineralization involved evaporitic salt and sedimentary organic-bearing units interacting through thermochemical sulfate reduction through the isotopic, mineralogy and inclusion evidences. Subsequently, the geology feature, mineral assemblages, EPMA data and isotopic values support the conclusion that the ore-forming hydrothermal fluids were mixed with magmatic hydrothermal fluids and forming the massive dark sphalerite, then yielding the calcite-quartz-sulfide vein ore type at the last stage. The genesis of this ore deposit was epigenetic rather than the previously-proposed sedimentary-exhalative(SEDEX) type.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

Effect of pedogenesis on the stable isotopic composition of calcretes and n‐alkanes: Implications for palaeoenvironmental reconstruction

In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ¹³C_PC and δ¹⁸O_PC) showed more variation compared with non‐pedogenic pond calcretes (δ¹³C_SPC and δ¹⁸O_SPC) in profile‐B. The δ¹³C_PC and δ¹³C_SPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ¹⁸O_PC and δ¹⁸O_SPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ¹³C_OM) and n‐alkanes (δ¹³C_n‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ¹³C_OM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ¹³C_OM values is a result of the difference in the sources and preservation of organic matter. However, the δ¹³C_n‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ¹³C_n‐alk values are unaffected by the pedogenic modifications.     

A Late‐glacial chironomid record from Hawes Water,northwest England

This paper presents the results of a high‐resolution Late‐glacial chironomid stratigraphy from Hawes Water, a small carbonate lake in northern Lancashire. The samples were from a core taken from the terrestrialised margin of the present lake, which represents an intermediate depth between the true littoral and the profundal. The chironomid assemblage showed a high degree of sensitivity to both broad‐scale and short‐term temperature changes. Comparison with an existing proxy temperature record (δ¹⁸O) for the site confirmed the presence of four temperature inversions within the Late‐glacial Interstadial. A mean July air temperature inference model, derived from acid, soft‐water lakes in Norway and Svalbard, was applied to the data. Despite the absence of carbonate lakes within the Norwegian training set, there was a close similarity between trends in estimated July air temperature and the δ¹⁸O trace, with a particularly strong correspondence in the periods of clay deposition. This suggests that this model is highly robust. The inferred maximum Interstadial temperature was 13.4°C, dropping initially to 7.5°C in the Loch Lomond Stadial. Temperatures reach a maximum of nearly 10°C in this period, cool for a short period before rising rapidly to 13.2°C at the start of the Holocene. These temperatures are similar to but slightly higher than those estimated for Whitrig Bog, southeast Scotland, and lower than those inferred from coleopteran‐based models for sites in South Wales. Copyright © 2004 John Wiley & Sons, Ltd.     

Geochemical Constraints on the Origin and Evolution of Spring Waters in the Changdu‐Lanping‐Simao Basin,Southwestern China

Chemical and isotopic data were measured for 51 leached brine springs in the Changdu-Lanping-Simao Basin (CD-LP-SM), China. The predominance of Cl and Na, saturation indices of carbonate minerals, and Na/Cl and Ca/SO4 ratios of ~1 suggest that halite, sulphate, and carbonate are the solute sources. Integration of geochemical, δ18O, and δD values suggests that springs are mainly derived from meteoric water, ice-snow melt, and water-rock interactions. B concentrations range from 0.18 to 11.9 mg/L, with δ11B values of ?4.37‰ to +32.39‰, indicating a terrestrial source. The δ11B-B relationships suggest B sources of crustal origin (marine carbonates with minor crust-derived volcanics); we did not identify a marine or deep mantle origin. The δ11B values of saline springs (+4.61‰ to +32.39‰) exceed those of hot (?4.37‰ to +4.53‰) and cold (?3.47‰ to +14.84‰) springs; this has contributed to strong water-rock interactions and strong saturation of dissolved carbonates. Conversely, the global geothermal δ11B-Cl/B relationship suggests mixing of marine and non-marine sources. The δ11B-Cl/B relationships of the CD-LP-SM are similar to those of the Tibet geothermal belt and the Nangqen Basin, indicating the same B origin. These differ from thermal waters controlled by magmatic fluids and seawater, suggesting that B in CD-LP-SM springs has a crustal origin.     

Seasonal temperatures from δ18O in recent Spanish tufa stromatolites: Equilibrium redux!

This study focuses on recent debate over the value of stable isotope‐based environmental proxies recorded in riverine tufa stromatolites. A twelve‐year record (1999 to 2012) of river‐bed tufa stromatolites in the River Piedra (north‐east Spain) was recovered in this study, along with a partly overlapping fifteen‐year record (1994 to 2009) of accumulations in a drainage pipe: both deposits formed in water with near identical physico/chemical parameters. Measured water temperature data and near‐constant δ ¹⁸O_water composition allowed selection of an ‘equilibrium’ palaeotemperature equation that best replicated actual temperatures. This study, as in some previous studies, found that just two published formulas for water temperature calculation from equilibrium calcite δ ¹⁸O compositions were appropriate for the River Piedra, where tufa deposition rates are high, with means between 5·6 mm and 10·8 mm in six months. The δ ¹⁸O_calcite in both the river and the pipe deposits essentially records the full actual seasonal water temperature range. Only the coldest times (water temperature <10°C), when calcite precipitation mass decreased to minimum, are likely to be unrepresented, an effect most noticeable in the pipe where depositional masses are smaller and below sample resolution. While kinetic effects on δ ¹⁸O_calcite‐based calculated water temperature cannot be ruled out, the good fit between measured water temperature and δ ¹⁸O_calcite‐calculated water temperature indicates that temperature is the principal control. Textural and deposition rate variability between the river and pipe settings are caused by differences in flow velocity and illumination. In the river, calcification of growing cyanobacterial mat occurred throughout the year, producing composite dense and porous laminae, whereas in the pipe, discontinuous cyanobacterial growth in winter promoted more abiogenic calcification. High‐resolution δ ¹⁸O_calcite data from synchronous pipe and river laminae show that reversals in water temperature occur within laminae, not at lamina boundaries, a pattern consistent with progressive increase in calcite precipitation rate as cyanobacterial growth re‐established in spring.     

Variations in the isotopic composition of molybdenum in freshwater lake systems

Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of ⁹⁷Mo/⁹⁵Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ⁹⁷Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ⁹⁷Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O₂ conditions in the bottom water through the Holocene indicates that increased O₂ concentrations are generally associated with low δ⁹⁷Mo/⁹⁵Mo values of the sediments, whereas lowered O₂ contents of the bottom water are accompanied by relatively high δ⁹⁷Mo/⁹⁵Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.