Modeling speleothem δC variability in a central Sierra Nevada cave using C and Sr/Sr

Carbon isotopes in speleothems can vary in response to a number of complex processes active in cave systems that are both directly and indirectly related to climate. Progressing downward from the soil zone overlying the cave, these processes include soil respiration, fluid-rock interaction in the host limestone, degassing of CO₂ and precipitation of calcite upflow from the speleothem drip site, and calcite precipitation at the drip site. Here we develop a new approach to independently constrain the roles of water-rock interaction and soil processes in controlling stalagmite δ¹³C. This approach uses the dead carbon proportion (dcp) estimated from coupled ¹⁴C and ²³⁰Th/U measurements, in conjunction with Sr isotope analyses on stalagmite calcite from a central Sierra Nevada foothills cave in California, a region characterized by a highly seasonal Mediterranean-type climate, to determine the roles of water-rock interaction and soil processes in determining stalagmite δ¹³C. Increases in stalagmite dcp between 16.5 and 8.8 ka are coincident with decreased δ¹³C, indicating a varying yet substantial contribution from the soil organic matter (SOM) reservoir, likely due to significantly increased average age of SOM in the soil veneer above the cave during wet climatic intervals.We use geochemical and isotope mixing models to estimate the host-carbonate contribution throughout the δ¹³C time series and determine the degree of degassing and calcite precipitation that occurred prior to precipitation of stalagmite calcite. The degree of degassing and prior calcite precipitation we calculate varies systematically with other climate indicators, with less degassing and prior calcite precipitation occurring during wetter climatic intervals and more during drier intervals. Modeled δ¹³C values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite δ¹³C values, even during relatively wet intervals. These results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem δ¹³C records, particularly those from caves that formed in seasonal semi-arid to arid environments.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

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.     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

Continental-scale patterns in modern wood cellulose δO: Implications for interpreting paleo-wood cellulose δO

The isotopic composition of ancient wood may be a useful archive of some climatic or geochemical conditions of the past, but presently there are many uncertainties that constrain such interpretations. We sampled naturally growing, predominantly native trees in forested regions of North America and the Caribbean to evaluate the strength of the relationships among cellulose δ¹⁸O (δ¹⁸O_cel), relative humidity (RH), precipitation δ¹⁸O (δ¹⁸O_ppt), and mean annual temperature (MAT) at the continental scale, and the general range of variability in δ¹⁸O_cel associated with site hydrologic conditions and species differences. We found up to 4‰ differences among different species growing at the same site, that conifer cellulose at a site is more enriched than angiosperm cellulose by 1.5‰ (p < 0.001), and that differences in landscape position, reflecting differing access to the water table, produced differences of <1‰ in δ¹⁸O_cel. At the continental scale, δ¹⁸O_cel was strongly influenced by modeled δ¹⁸O_ppt (R² = 0.80, p < 0.001). Average summer minimum RH (RH_min) combined with δ¹⁸O_ppt explained more of the variability (R² = 0.93, p < 0.001) in δ¹⁸O_cel across North American and Caribbean forests. MAT and δ¹⁸O_cel were also strongly correlated across North America (R = 0.91 and 0.95, p < 0.001, for angiosperms and conifers, respectively). The difference between δ¹⁸O_ppt and δ¹⁸O_cel is not constant (varying from 35-44‰) and is inversely correlated with δ¹⁸O_ppt. The relationships among δ¹⁸O_ppt, RH_min, δ¹⁸O_cel, and MAT established for North America and the Caribbean applied reasonably well when δ¹⁸O_cel was used to estimate MAT and δ¹⁸O_ppt in Asia, Europe, and South America, but there were important exceptions. The most accurate predictions of MAT and δ¹⁸O_ppt from δ¹⁸O_cel require RH_min. Predictions of δ¹⁸O_ppt and MAT made from δ¹⁸O_cel alone produced errors of up to 8‰ and 16 °C, respectively.     

Development and application of diffusive gradients in thin films for determining inorganic arsenic concentrations in natural waters

In environmental systems arsenic exists in both inorganic and organic forms. These forms differ substantially with respect to their toxicity as inorganic forms of arsenic are generally more toxic than organic forms. A novel method for in-situ inorganic ar…     

Hydrological budget,carbon sources and biogeochemical processes in Lac Pavin (France): Constraints from δO of water and δC of dissolved inorganic carbon

Lac Pavin (French Massif Central) is a permanently stratified lake: the upper water layers (mixolimnion, from 0 to 60 m depth) are affected by seasonal overturns, whereas the bottom water layers (monimolimnion, from 60 to 90 m depth) remain isolated and are never mixed. Hence, they are capable of storing important quantities of dissolved gases, mainly CO₂. With the aim of better constraining the water balance and of gaining new insights into the carbon cycle of Lac Pavin, an isotopic approach is used. The δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ profiles lead the authors to give a new evaluation of the evaporation flow rate (8 L s⁻¹), and to propose and characterize two sub-surface springs. The sub-surface spring located at the bottom of the lake can be deduced from the 1% isotopic difference between the upper water layers (mean δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ value: −7.3‰) and the bottom water layers (δ¹⁸OH₂O=-8.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-8.4‰$). It is argued that this sub-surface spring has isotopic and chemical characteristics similar to those of the magmatic CO₂-rich spring (i.e. Fontaine Goyon, δ¹⁸OH₂O=-9.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-9.4‰$), and we calculate its flow rate of 1.6 L s⁻¹. The second sub-surface spring is located around 45 m depth, with a composition close to those of the water surface streams (δ¹⁸OH₂O<-7.6‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}<-7.6‰$).     

Compound- and enzyme-specific phosphodiester hydrolysis mechanisms revealed by δO of dissolved inorganic phosphate: Implications for marine P cycling

We have studied the oxygen isotope signature of inorganic phosphate (P_i) generated by hydrolysis of nucleic acid phosphodiester (P-diester) compounds by cell-free enzymes (Deoxyribonuclease 1, Phosphodiesterase 1, Alkaline phosphatase) and microbial cultures at natural isotopic abundances. We demonstrate that the diesterase-catalyzed hydrolytic step leads to incorporation of at least one water O into released P_i for a total of two O atoms from water incorporated into P_i released from P-diesters. In the presence of Phosphodiesterase 1, ¹⁶O is preferentially incorporated into nucleotides released from DNA; whereas ¹⁸O is preferentially incorporated into nucleotides released from RNA. A strong consistency between predicted O-isotope regeneration signatures based on results of cell-free enzyme experiments and measured isotopic signatures from independent experiments with E. coli cultures was observed and confirms proposed models for phosphoester hydrolysis. Results from these studies made at natural ¹⁸O abundance levels provide a new tool, enzyme-specific O-isotope fractionation, for investigations of organophosphate metabolism and phosphorus cycling pathways in natural aquatic systems.     

Speleothem calcite farmed in situ: Modern calibration of δO and δC paleoclimate proxies in a continuously-monitored natural cave system

Understanding the relationships between speleothem stable isotopes (δ¹³C δ¹⁸O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ¹⁸O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ¹⁸O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s⁻¹ in winter and 0.4 m s⁻¹ in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO₂. A clear relationship is found between calcite δ¹³C and cave air ventilation rates estimated by proxies pCO₂ and ²²²Rn. Calcite δ¹³C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ¹³C_CaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ¹³C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ¹³C records in ancient speleothems. Calcite δ¹³C_CaCO3 may be a proxy not only for atmospheric CO₂ or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ¹⁸O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ¹³C_CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ¹⁸O_CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments:

1000lnα=16.1(10³T^-1)-24.6     

Palaeocene–Eocene carbon isotopic excursion from the shallow-marine-carbonate sequence of northeast India: Implications on the CIE magnitude and geometry

The exact magnitude of the carbon isotopic excursion (CIE) for the Palaeocene–Eocene Thermal Maximum (PETM) is essential for our understanding of the carbon cycle perturbation. Global compilation of the PETM CIE magnitudes indicates that the shallow-marine inorganic carbonate could be a potential candidate to decipher the actual CIE magnitude. The present study, therefore, made an attempt to explore the thick Palaeogene shallow-marine carbonate sequence of the Sylhet Limestone exposed in the Jaintia Hills of northeast (NE) India, in terms of the preservation and magnitude of the PETM CIE. Exploratory sampling carried out across the Sylhet Limestone suggests that this sequence was deposited during the Late Palaeocene and Early Eocene, as evident from the age-diagnostic foraminifera. The observed \({\sim }3.4\permille \) CIE at the top of the Lakadong Limestone, resting above the Miscellanea miscella and Ranikothalia nuttalli foraminifera-bearing horizon, can, therefore, be correlated with the PETM CIE. Although the magnitude of the CIE from our limited data set agrees well with the global compilation, the absence of a stepped profile questions the preservation of the CIE reported elsewhere from the Tethyan sequence. Further work is needed for a better understanding of the PETM interval in NE India.     

Methane with Abnormally High δ13C and δD Values from the Coastal Hot Springs in Lake Baikal

Lithology and Mineral Resources - We studied the composition and isotopic characteristics (δ13C and δD) of hydrocarbon gases from the Kotelnikovsky, Zmeiny, and Goryachnisky hot springs...     

Li and δLi in mudrocks from the British Caledonides: Metamorphism and source influences

Mudrocks from three lower Paleozoic basins in the British Caledonides (southern Lake District, northern Lake District and Southern Uplands) were investigated to determine the influence of sub-greenschist facies metamorphism on Li and the factors that control Li in fine-grained terrigenous sedimentary rocks. Metamorphic grade, as determined by KI (Kübler index) does not correlate with Li content ([Li]) and δ⁷Li, indicating that sub-greenschist facies metamorphism has negligible effect on Li in these rocks. Collectively, the data for all three basins show a negative correlation between [Li] and δ⁷Li and a positive correlation between [Li] and the Chemical Index of Alteration (CIA), suggesting that provenance exerts the greatest control on Li in mudrocks. Samples from the northern Lake District, which were deposited in an extensional basin, have homogeneous REE patterns, similar to shale composites (PAAS), the highest CIA, Th/U and [Li] and the lowest δ⁷Li and ε_Nd, consistent with their derivation from a highly weathered, ancient continental source. By contrast, mudrocks from the Southern Uplands range to the lowest CIA, Th/U and [Li] and have the highest δ⁷Li and ε_Nd. These samples were deposited in a forearc basin on the southern margin of the Laurentian craton and contain volcanic detritus. Their REE patterns are the most variable, ranging from average shale-like patterns to less LREE-enriched patterns. The compositional heterogeneity within the Southern Uplands mudrocks is consistent with a mixed provenance that includes juvenile crustal materials (lower [Li], ε_Nd and Th/U, higher δ⁷Li), likely derived from the arc, as well as more highly weathered continental detritus. Mudrocks from the southern Lake District were deposited in a foreland basin, and exhibit geochemical characteristics intermediate between the northern Lake District and the Southern Uplands mudrocks, indicating their derivation from a mixed source. Our study shows that Li concentrations and δ⁷Li can provide additional information on the degree of weathering of the provenance of mudrocks.     

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

Stable nitrogen and carbon isotope (δN and δC) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ¹⁵N and δ¹³C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ¹⁵N and δ¹³C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ¹⁵N and δ¹³C values between sites was present. Skeletal δ¹⁵N values significantly increased and δ¹³C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of −0.013‰ m⁻¹ and +0.023‰ m⁻¹ are recommended for δ¹⁵N and δ¹³C, respectively. Average depth-corrected δ¹⁵N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ¹³C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ¹³C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ¹⁵N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ¹⁵N record, and suggests that these corals may be useful for δ¹⁵N-based paleoceanographic reconstructions. Variability in δ¹³C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ¹⁵N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ¹³C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Response of biomass accumulation and nodulation by Vicia villosa to soil conditions: Evidence from δ13C and δ15N isotopes

Vicia villosa is an annual legume plant,and is mainly used for green manure by farmers in southwest China.Field growth experiments were performed on six plots.The concentrations of mineral nutrients and soluble sugar,and the changes of carbon and nitrogen isotopic composition within and among organs of Vicia were deter- mined.Significant differences in legume growth were found in response to soil type and its moisture conditions.The Vicia villosa was relatively well adapted to growth in limestone soils than sandstone soils.The distribution of sugar concentrations andδ1 3C-differences between roots and leaves indicate that the translocation of sugars from leaves to roots may be restricted by soil drought.Therefore,there was an inhibition of Pi distribution from roots to leaves, resulting in over optimum threshold of N/P ratio.Those may originate from the feedback regulation in the legume, where soluble sugar could not be distributed from leaves to roots.The results ofδ1 5N values in tissues suggest that there should be different preferential use of nitrogen resource by legume during the formation of nodules:before nodule formation the legume preferentially utilizes inorganic nitrogen from soils,but afterwards the nitrogen should be mainly from N2-fixation.Our results indicate that the lack of nodulation development,except for S2,should be ascribed to the factor controlling bi-direction nutrient transfer,which should be efficiency of establishment symbiosis with arbuscular mycorrhiza before nodulation formation.It is predicted that the species of Vicia villosa should be a legume associated with dual symbiosis with rhizobia and mycorrhiza.     

A 35 kyr record of organic matter composition and δ13C of n-alkanes in bog sediments close to Lake Baikal: Implications for paleoenvironmental studies

We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C₂₄ to C₃₀ alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C₂₇ to C₃₃ alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C₂₄ to C₃₀ alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C₂₄ to C₃₀ alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ¹³C values of n-C₂₇ to C₃₃ alkanes (e.g. ?29‰ to ?33‰ for C₃₁) indicate the presence of C₃-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C₂₇ to C₃₃ alkane parameter are generally higher than those using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.     

Intra-shell boron isotope ratios in the symbiont-bearing benthic foraminiferan Amphistegina lobifera: Implications for δB vital effects and paleo-pH reconstructions

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ¹¹B has some limitations such as the knowledge of the fractionation factor (α_4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α_4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ¹¹B (Δ¹¹B) for each seawater pH. This Δ¹¹B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α_4-3, or the δ¹¹B_sw through time. It may also be independent of the pK_B (the dissociation constant of boric acid) value. Therefore, Δ¹¹B in foraminifera can potentially reconstruct paleo-pH of seawater.     

Chemical and strontium isotopic characteristics of shallow groundwater in the Ordos Desert Plateau,North China: Implications for the dissolved Sr source and water–rock interactions

In this study, the chemical and Sr isotopic compositions of shallow groundwater and rainwater in the Ordos Desert Plateau, North China, and river water from the nearby Yellow River, are investigated to determine the dissolved Sr source and water–rock interactions, and quantify the relative Sr contribution from each end-member. Three groundwater systems have been identified, namely, GWS-1, GWS-2 and GWS-3 according to the watershed distribution in the Ordos Desert Plateau. Ca²⁺ and Mg²⁺ are the most dominant cations in GWS-1, while Na⁺ is dominant in GWS-3. In addition, there is more SO₄²⁻ and less Cl⁻ in GWS-1 than in GWS-3. The shallow groundwater in GWS-2 seems to be geochemically between that in GWS-1 and GWS-3. The ⁸⁷Sr/⁸⁶Sr ratios of the shallow groundwater are high in GWS-1 and GWS-2 and are low in GWS-3. By geochemically comparing the nearby Yellow River, local precipitation and deep groundwater, the shallow groundwater is recharged only by local precipitation. The ionic and isotopic ratios indicate that carbonate dissolution is an important process controlling the chemistry of the shallow groundwater. The intensity of the water–rock interactions varies among the three groundwater systems and even within each groundwater system. Three end-members controlling the groundwater chemistry are isotopically identified: (1) precipitation infiltration, (2) carbonate dissolution and (3) silicate weathering. The relative Sr contributions of the three end-members show that precipitation infiltration and carbonate dissolution are the primary sources of the shallow groundwater Sr in GWS-3 whereas only carbonate dissolution is responsible for the shallow groundwater Sr in GWS-1 and GWS-2. Silicate weathering seems insignificant towards the shallow groundwater's chemistry in the Ordos Desert Plateau. This study is helpful for understanding groundwater chemistry and managing water resources.     

Compound specific δD values of long chain n-alkanes derived from terrestrial higher plants are indicative of the δD of meteoric waters: Evidence from surface soils in eastern China

The stable carbon and hydrogen isotope composition of higher plant-derived long chain n-alkanes (δ¹³C_n-alkanes and δD_n-alkanes) from 45 surface soil samples (within well characterized vegetation zones) from eastern China (18°N–50°N) are reported. The weighted average δD_n-alkanes value for n-C₂₇, n-C₂₉ and n-C₃₁ in the samples and the annual average δD of meteoric water recorded at 12 weather stations proximal to the sampling sites show similar spatial variations. The δD of n-alkanes shows a gradual depletion in value with increasing latitude. The results demonstrate that, on a large spatial scale, the δD values of long chain n-alkanes derived from higher plants have the potential to record the δD of meteoric water, although many other factors can also influence the isotope values. There appears to be no apparent relationship between the δD of the n-alkanes extracted from the surface soil and the overlying vegetation type (i.e. forest/grassland or C₃/C₄ composition). Therefore, palaeoenvironmental studies utilizing δD_n-alkanes from higher plant-derived material in geological samples have the potential to provide additional information with regard to the past hydrological cycle.