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 laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments

An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α_{(silica-water)} = 2.39(±0.13) × 10⁶T⁻² + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a ‘vital’ effect, where the δ¹⁸O value of the water inside the diatom cell walls is lower than the δ¹⁸O values of ambient water.Post-mortem loss of organic material results in an alteration or ‘maturation’ of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ¹⁸O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with bottom conditions could reduce or remove the conflating effects of temperature on δ¹⁸O values recorded by paleo-diatom silica and provide direct information on the δ¹⁸O value of the lake water.     

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.     

湖泊硅藻氧同位素:一种前景广阔的陆相古气候指标

硅藻氧同位素已日益成为陆相古气候重建的一种重要手段。文章在简述这一领域已取得的基本认识基础上,着重介绍了近年来的重要进展。主要进展包括: 1)在硅藻的分离纯化方面,规范了重液分离法和新的重力差异流体分离法;2)完善了分步氟化法,创生了高温碳还原法的氧同位素制取技术;3)通过实验培养和天然湖泊监测实验,证实了硅藻氧同位素与温度的分馏平衡关系;4)湖泊硅藻氧同位素可以反映古温度、气候干旱事件和大气降水来源变化。同时,对目前硅藻氧同位素在湖泊沉积古气候研究中存在的主要问题作了讨论和展望。     

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

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

Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition

Aiming at developing a novel tool for palaeoclimate research, we recently proposed a new method for determining the oxygen isotope composition of monosaccharides (Zech, M., Glaser, B., 2009. Compound-specific δ¹⁸O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Communications in Mass Spectrometry 23, 3522–3532). In order to answer the question whether isotope fractionation and oxygen exchange reactions during litter decomposition affect the climatically controlled δ¹⁸O values of plant derived sugars, such as for instance xylose and arabinose from hemicelluloses, we studied the compound specific δ¹⁸O values of five different litter species having been decomposed in a field litterbag experiment for 27 months.While δ¹⁸O values of bulk organic matter yielded a systematic ¹⁸O depletion of 3.3‰ (pine) to 4.6‰ (spruce) accompanying total cellulose decomposition of 51% (beech) to 86% (ash), δ¹⁸O values of individual sugars show no significant trend with time. In addition to the observed absence of isotope fractionation during decomposition, we also rule out ¹⁸O exchange reactions affecting the δ¹⁸O signature of sugar molecules during diagenetic processes as well as during analytical procedure based on experimental findings and on theoretical biochemical mechanistic considerations. We conclude that our new method may become an analytical tool that elegantly overcomes extraction, purity and hygroscopicity problems of previous ¹⁸O cellulose methods. It furthermore has the potential to be applied to a wide range of climate archives such as tree rings, lacustrine sediments and loess palaeosol sequences.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Brine formation recorded by stable isotopes of Recent benthic foraminifera in Storfjorden,Svalbard: palaeoceanographical implications

We discuss water oxygen isotopes (δ¹⁸O_w) and carbon isotopes of dissolved inorganic carbon (δ¹³C_DIC) of brine‐enriched shelf water (BSW) from Storfjorden (southern Svalbard) in comparison to Recent benthic foraminiferal δ¹⁸O_c and δ¹³C_c calcified in the same water. We determined relatively high δ¹⁸O_w values of 0.15±0.03‰ VSMOW in BSW below sill depth at temperatures below ?1.8 °C, and high δ¹⁸O_c values of 3.90±0.18‰ VPDB. Such high BSW δ¹⁸O_w cannot significantly deplete ¹⁸O_w contents of Arctic Ocean deep water; furthermore, such high δ¹⁸O_c cannot be distinguished from δ¹⁸O_c values of 3.82±0.12‰, calcified in warmer Arctic and Nordic seas intermediate and deeper waters. Today, in Storfjorden low benthic δ¹³C_c and high δ¹⁸O_c reflect the low δ¹³C_DIC and relatively high δ¹⁸O_w of BSW. High benthic δ¹⁸O_c is in contrast to expected low δ¹⁸O_c as brine rejection is widely thought to predominantly take place in surface water diluted by meteoric water with very low δ¹⁸O_w. Low epibenthic δ¹³C_c values of 0.50±0.12‰ partly reflect low δ¹³C_DIC caused by enhanced uptake of atmospheric low δ¹³C_CO2 decreased by anthropogenic activities. An adjustment for preindustrial higher values would increase δ¹³C_c by about 0.6‰. Therefore, in Storfjorden brine formed before the industrial era would be characterized by both high δ¹³C_c as well as high δ¹⁸O_c values of benthic foraminiferal calcite. Our data may cast doubt on scenarios that explain negative excursions in benthic foraminiferal stable isotope records from the Atlantic Ocean during cold stadials in the last glacial period by enhanced brine formation in Nordic seas analogously to modern processes in Storfjorden.     

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

Isotope geochemistry (O, C, S, Sr) and Rb-Sr age of carbonatites in central Tuva

The Rb-Sr isochron age of igneous ankerite-calcite and siderite carbonatites in central Tuva is estimated at 118 ± 9 Ma. The following ranges of initial values of O, C, Sr, and sulfide and S isotopic compositions were established: δ¹⁸O_carb = +(8.8?14.7)‰, δ¹³C_carb = ?(3.6?4.9)‰, δ¹⁸O_quartz = +(11.6?13.7)‰, δ³⁴S_pyrite = +(0.3?1.1)‰, and (⁸⁷Sr/⁸⁶Sr)_i =0.7042?0.7048 for ankerite-calcite carbonatite and δ¹⁸O_sid = +(9.2?12.4)‰, δ¹³C_sid = ?(3.9?5.9)‰, δ¹⁸O_quartz = +(11.2?11.4)‰, δ³⁴S_pyrite = ?(4.4–1.8)‰, δ³⁴S_sulfate = +(8.6?14.5)‰, and (⁸⁷Sr/⁸⁶Sr)_i = 0.7042?0.7045 for siderite carbonatite. The obtained isotopic characteristics indicate that both varieties of carbonatites are cognate and their mantle source is comparable with the sources of Late Mesozoic carbonatites in the western Transbaikal region and Mongolia. The revealed heterogeneity of isotopic compositions of carbonatites is caused by their contamination with country rocks, replacement with hydrothermal celestine, and supergene alteration.     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

Effect of network-forming cations on the oxygen isotope fractionation between silicate melts: Experimental study at 1400–1570°C

We have experimentally studied the behavior of oxygen isotope composition in silicate melts with a wide range of network-forming cations. Isotopic equilibration of the Di-An eutectic melts modified by addition of Si, Al, Ti, and Fe was carried out in a vertical tube furnace within a temperature range from 1400 to 1570°C. It was established that the value ^{10 3}Lnα between silicic and basic melts at 1400 and 1450°C systematically increases with increase of SiO₂ content, reaching ≈1‰ at 20% melt silica enrichment. The effect of the Fe₂O₃, TiO₂, and Al₂O₃ contents was studied at 1500°C. An increase in Fe₂O₃ from 5 to 20 wt % causes a 0.4‰ increase of δ¹⁸O. An increase in Ti and Al contents results in the non-linear behavior of δ¹⁸O, which decreases in the region of the highest TiO₂ (28.4%) and Al₂O₃ (29.3 %) contents. In the region of moderate Fe₂O₃, TiO₂, and Al₂O₃ contents, the values of δ¹⁸O show monotonous linear dependence on the oxide contents. Methods of estimations of oxygen isotope fractionation coefficients at T > 1400°C in the studied range of network-forming oxides are considered on the basis of experimental data. The calculation of fractionation coefficients with the use of I¹⁸O index showed that experimental values with increase of SiO₂ content deviate from calculated values by 0.3‰ for basic melts and 0.5–0.6‰ in the region of silicic melts. Similar pattern is observed during approximation of a melt by normative mineral composition. The calculation with the Garlick index leads to the systematic underestimation (on average, by 0.3‰) of 10³Lnα as compared to the experimental data. The NBO/T ratio appeared the best parameter to describe 10³Lnα in the melt-melt system, including the region of high-Fe melts. Analysis of experimental data leads us to conclude that the degree of polymerization of the melts in the studied temperature-composition region is the most important factor affecting the oxygen-isotope fractionation in the melt-melt system. Empirical index similar to the Garlick index was proposed to take into account oxygen associated with T-cations: $$I^m = (C_{Si} + aC_{Al} + bC_{Ti} + cC_{Fe^{3 + } } )/\Sigma C_i ,$$ where a, b, and c constants are empirically established coefficients: 0.75, 0. 70, and 1.75, respectively.     

Isotopic composition of cellulose from aquatic organisms

The stable isotopic ratios of oxygen, carbon and the non-exchangeable carbon-bound hydrogen of cellulose from marine plants (algae and higher vascular forms) and animals (tunicates) collected in their natural habitats and from freshwater vascular plants grown in the laboratory under controlled conditions were determined.The δ¹⁸Ovalues of cellulose from all the plants and animals were 27 ±3% more positive than the δ¹⁸O values of the waters in which the organisms grew. Temperature had little or no influence on this relationship for three species of freshwater vascular plants that were analyzed. The relationship between the δ¹⁸O values of cellulose and the water used in its synthesis is probably established by the isotopic fractionation that occurs during the hydration of carbonyl groups of the intermediates involved in cellulose synthesis.The δD values of the non-exchangeable hydrogen of cellulose (determined by analyzing cellulose nitrate) from different organisms that grew in the same environment differed by large amounts. This difference ranged up to 200‰ for different species of algae collected at a single site: the corresponding difference for different species of tunicates and vascular plants was 60 and 20‰ respectively. The δD values of cellulose nitrate from different species of freshwater vascular plants grown in water of constant temperature and isotopic composition differed by as much as 60‰ The relationship between the δD values of the carbon-bound hydrogen of cellulose and the water used in its synthesis displayed a significant temperature dependence for four species of freshwater vascular plants that were analyzed. The δD values of cellulose nitrate prepared from different parts of one of the plants grown under constant conditions differed by 40‰ Hydrogen isotopic fractionation during cellulose synthesis appears to be more variable among different species and displays a larger temperature dependence than was suggested by previous studies.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

The oxygen isotopic composition of phosphate as an effective tracer for phosphate sources in Hongfeng Lake

In order to characterize the oxygen isotopic composition of internal phosphate and explore the possibility of using these data to identify phosphate sources, we measured oxygen isotopic compositions of phosphate (δ¹⁸O_p) in sediment pore water in Hongfeng Lake, a typical deep-water lake in a mountainous area. These data, in combination with δ¹⁸O_p in surface water samples and water column samples, were successfully used to identify phosphate sources. The δ¹⁸O_p value of sediment pore water ranged from 15.2‰ to 15.8‰, with an average value of 15.5‰—the δ¹⁸O_p value of internal phosphate. The δ¹⁸O_p values decreased gradually through the water column from 19.4‰ in surface water to 16.4‰ in deeper water, implying that internal phosphate had more negative δ¹⁸O_p values than external phosphate. This finding was substantiated by horizontal variations in δ¹⁸O_P values, which decreased with increasing distance from inflowing rivers. All collected evidence suggests that external and internal phosphate have distinctly different isotopic signatures and that these signatures have not been considerably altered by biological mediation in Hongfeng Lake. Therefore, δ¹⁸O_P can be used to distinguish phosphate sources. A two-endmember mixing model showed that internal phosphate had an average contribution of 40%, highlighting the influence of internal phosphorus loading on aqueous phosphate and eutrophication. This study illustrates the need to reduce the internal phosphorus load from sediment and provides guidance for nutrient management and in-lake restoration treatment in Hongfeng Lake. The data presented here are limited, but serve to highlight the great potential of δ¹⁸O_p as an effective tracer for identifying phosphate sources. Systematic investigations of the oxygen isotopic compositions of external phosphate, internal phosphate, and phosphate through the water column, in combination with in-lake P biogeochemical cycle study, would be desirable in further research.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Controls on the stable isotope composition of seasonal growth bands in aragonitic fresh-water bivalves (unionidae)

Water temperature, oxygen isotope composition and the δ¹³C of dissolved inorganic carbon were measured in 2 southern Michigan rivers, the Huron River and Fleming Creek, between late September 1990 and June 1992. The final full year of shell growth in 3 unionids collected in 1992 from these rivers was sampled for stable isotope analysis with a resolution of 30 μm. The δ¹⁸O of both shell nacre and the prismatic layer is accurately predicted by a fractionation relationship developed for biogenic aragonite. High resolution sampling of 3 species and bulk sampling of 3 other species suggest that all unionids adhere to this oxygen isotope fractionation relationship. This relationship is used to show that shell growth ceases below approximately 12°C. In these 2 settings the average δ¹⁸O value of shell (PDB scale) is within 0.5‰ of the average δ¹⁸O of river water (SMOW scale). Unionids can therefore be used in oxygen-isotope-based paleoclimatic and paleohydrologic reconstructions. In contrast, the carbon isotope ratio of shell is not accurately predicted by published fractionation factors between D.I.C. and carbonate. Shell δ¹³C is more negative than predicted values and the offset is highly variable suggesting a significant and variable incorporation of metabolic carbon into the shell carbonate.