Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

Climate change during the past 1000 years: a high‐temporal‐resolution multiproxy record from a mire in northern Finland

We present a record of peatland development in relation to climate changes and human activities from the Palomaa mire, a remote site in northern Finland. We used fine‐resolution and continuous sampling to analyse several proxies including pollen (for vegetation on and around the mire), testate amoebae (TA; for mire‐wetness changes), oxygen and carbon isotopes from Sphagnum cellulose (δ¹⁸O and δ¹³C; for humidity and temperature changes), peat‐accumulation rates and peat‐colour changes. In spite of an excellent accumulation model (30 ¹⁴C dates and estimated standard deviation of sample ages <1 year in the most recent part), the potential to determine cause–effect (or lead–lag) relationships between environmental changes and biotic responses is limited by proxy‐specific incorporation processes below the actively growing Sphagnum surface. Nevertheless, what emerges is that mire development was closely related to water‐table changes rather than to summer temperature and that water‐table decreases were associated with increasing peat‐accumulation rates and more abundant mire vegetation. A rapid fen‐to‐bog transition occurred within a few years around AD 1960 when the water table decreased beyond the historical minimum, supporting the notion that mires can rapidly shift into bogs in response to allogenic factors. Copyright © 2012 John Wiley & Sons, Ltd.     

Isotopic compositions of S, N and C in soils and vegetation of three forest types in Québec, Canada

The concentrations and the isotopic compositions of S, N and C were studied in soils and in the dominant plant species of three forested watersheds (Québec, Canada) located along a latitudinal and atmospheric deposition gradient. Large increases in S, N and C isotope ratios (up to 3.9‰, 10‰, 2.6‰, respectively) were observed with increasing soil depth at the three watersheds. These increases were accompanied by a strong decrease in elemental concentrations resulting in a strong negative relationship between these two variables. Both S and N concentrations throughout the soil profile and δ³⁴S and δ¹⁵N in the mineral soil appeared to increase with increasing S and N deposition rates and decreasing latitude. A strong positive linear relationship was found between δ³⁴S and δ¹⁵N (R² = 0.72) values and between organic S and N concentrations (R² = 0.96) in soils. The slope of the linear relationship between δ³⁴S and δ¹⁵N (δ³⁴S = f(δ¹⁵N)) indicated that isotopic fractionation was almost 4 times higher for S than for N during transformations that occurred in soil. However, this difference might reflect a higher degree of openness of the S cycle compared to the N cycle rather than an isotope effect per se. Overall, the results suggest that N and S inputs significantly impact the isotope ratios and the concentrations of N and S in the soils, and that S and N were closely associated and subject to similar processes with the same isotopic effects throughout the soil profile. Contrary to most studies, δ³⁴S-SO₄ in stream water of the most northerly site with the lowest S deposition rate was significantly higher than δ³⁴S-SO₄ in atmospheric depositions but similar to the δ³⁴S of the bulk mineral soil. It suggests that the mineral soil actually contributes a large portion of the stream S-SO₄ for this site.     

Elemental and isotopic carbon and nitrogen records of organic matter accumulation in a Holocene permafrost peat sequence in the East European Russian Arctic

A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (～2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ¹⁵N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ¹³C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ¹⁵N and δ¹³C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed ¹⁵N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.     

Modelling fractionation of stable isotopes in stalagmites

High resolution δ¹³C and δ¹⁸O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ¹³C and δ¹⁸O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water p_CO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ¹³C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ¹⁸O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ¹⁸O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ¹⁸O values on drip interval. The temperature dependence of δ¹⁸O, however, is more pronounced than for δ¹³C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ¹³C and δ¹⁸O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ¹³C values along an individual growth layer.     

A proxy record of late Holocene climate change from May Moss,northeast England

Quantitative reconstruction of changes in mire surface wetness has been used to reconstruct proxy climate from an upland ombrotrophic blanket mire on the North York Moors in northeast England (May Moss). Testate amoebae, plant macrofossil and humification analyses were carried out for six peat profiles. Transfer functions are used to generate estimates of water table levels from the testate amoebae stratigraphy, which complement the semi‐quantitative indications of changing surface wetness provided by plant macrofossil and humification analysis. ¹⁴C dates provide the chronology for the stratigraphy. Differences were encountered between AMS ¹⁴C dates on pure Sphagnum remains and radiometric dates on bulk peat from the same horizon, which perhaps arise from the heterogeneity of peat. Replicate palaeoecological analysis of adjacent cores identifies consistency within testate amoebae and plant macrofossil stratigraphies, and reveals a strong agreement between the water table level proxies. The record of hydrological changes at sites across May Moss are in synchrony, and so climate change is the most likely cause of the moisture fluctuations. Changes to a wetter or cooler climate were identified cal. ad 260–540, ca. ad 550–650, cal. ad 670–980, ca. ad 1350–1450, cal. ad 1400–1620 and ca. ad 1700–1800. Periods with a drier or warmer climate precede all of these wet shifts, with particularly dry periods between cal. ad 650–860 and 690–980 and between cal. ad 1290–1410 and 1400–1620. Copyright © 2001 John Wiley & Sons, Ltd.     

Isotopic geochemistry of burial-metamorphosed volcanogenic sediments,Great Valley sequence,northern California

Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ¹⁸O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ¹⁸O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ¹⁸O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ¹⁸O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ¹³C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCO^t-₃ was continuously enriched in ¹³C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ¹⁸O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

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.     

Do drifts deposited adjacent to carbonate platforms record the signal of global carbon isotopic values?

This study investigates the δ¹³C values of Middle Miocene–Modern drift deposits and periplatform sediments in the Maldives and compares these data with the global δ¹³C values derived from bulk oceanic sediments and foraminifera. This comparison reveals that while the δ¹³C values of the early Miocene periplatform sediments in the Maldives appear to track the global record of δ¹³C values, including increases associated with the Oligocene–Miocene boundary as well as the variations within the Monterey Event, the correlation with the Monterey Event may be coincidental. It is suggested that variations in δ¹³C values do not reflect changes in oceanic dissolved inorganic carbon, but instead pulses of sediment arising from platform progradation that contribute carbonates with elevated δ¹³C values derived from the adjacent shallow‐water atolls. This conclusion is supported both by correlations between the seismic sequence architecture and the δ¹³C values which document progradation of ¹³C‐rich platform sediments, and also by the continuation of the interval of ¹³C‐rich sediments past the end of the Monterey Event at 13 Ma within the drift.     

A 15 000‐year record of climate change in northern New Mexico,USA, inferred from isotopic and elemental contents of bog sediments

Elemental (C, N, Pb) and isotopic (δ¹³C, δ¹⁵N) measurements of cored sediment from a small bog in northern New Mexico reveal changes in climate during the Late Pleistocene and Holocene. Abrupt increases in Pb concentration and δ¹³C values ca. 14 420 cal. YBP indicate significant runoff to the shallow lake that existed at that time. Weathering and transport of local volcanic rocks resulted in the delivery of Pb‐bearing minerals to the basin, while a ¹³C‐enriched terrestrial vegetation source increased the δ¹³C values of the sedimentary material. Wet conditions developed over a 300 a period and lasted for a few hundred years. The Younger Dryas period (ca. 12 700–11 500 cal. YBP) caused a reduction in terrestrial productivity reflected in decreasing C/N values, δ¹⁵N values consistently greater than 0‰ and low organic content. By contrast, aquatic productivity increased during the second half of this period, evidenced by increasing δ¹³C values at the time of highest abundance of algae. Dry conditions ca. 8 000–6 000 cal. YBP were characterised by low organic carbon content and high Pb concentrations, the latter suggesting enhanced erosion and aeolian transport of volcanic rock. The range in δ¹³C, δ¹⁵N and C/N values in the sedimentary record fall within the range of modern plants, except during the periods of runoff and drought. The sedimentary record provides evidence of natural climate variability in northern New Mexico, including short‐ (multi‐centennial) and long‐(millennial) term episodes during the Late Pleistocene and Holocene. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of detrital carbonate on stable oxygen and carbon isotope data from varved sediments of the interglacial Piànico palaeolake (Southern Alps,Italy)

Contamination with detrital matter is a well‐known bias in δ¹⁸O records from lake carbonates but quantitative information of this effect is yet lacking. Therefore, we developed a new methodological approach combining isotope analyses with microfacies, X‐ray diffraction and micro‐X‐ray fluorescence data and applied this in a case study for the Piànico interglacial lake record in order to provide a quantitative estimate of the effect of detrital carbonate on stable δ¹⁸O and δ¹³C data. The Piànico record contains a long series of distinct and well‐preserved calcite varves and is correlated to Marine Isotope Stage 11. Intercalated in the varve sequence are detrital layers triggered by surface erosion events. These detrital layers are mainly composed of dolomite, thus reflecting the mineralogical signature of the catchment. Microfacies analyses of a 9350 varve year interval allows the identification of detrital layers down to sub‐millimetre scale and a precise selection of three different types of samples for isotope analyses: (1) pure endogenic calcite varves (five varves per sample) without detrital contamination; (2) individual detrital layers; and (3) ‘mixed’ samples including five calcite varves and up to four thin detrital layers. Detrital samples show the isotopic signature of the catchment dolomite and are up to 5.7‰ enriched in δ¹⁸O values with respect to endogenic calcite samples. In mixed samples, the degree of isotopic enrichment is directly related to the amount of detrital contamination; δ¹⁸O of bulk carbonates is significantly biased when the detrital component amounts to more than 5% of the sample. It is also shown that samples containing detrital material have an influence on the calculation of the covariance between δ¹³C and δ¹⁸O. Covariance is high (r = 0.76) when the correlation coefficient is calculated on the base of all samples, but absent (r = ?0.43) when samples containing detrital dolomite are excluded. It has been demonstrated that microfacies analysis is a quick tool to avoid or reduce detrital contamination in bulk carbonate samples during sample selection. Copyright © 2009 John Wiley & Sons, Ltd.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Geochemistry, Monazite U–Pb Dating, and Li–Nd Isotopes of the Madi Rare Metal Granite in the Northeastern Part of the North China Craton

The Madi rare metal granite is a complex massif, which contains a variety of rare metals, such as Nb, Ta, Li, and Be. In this paper, the geochemical characteristics of the granite were obtained by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). The precise crystalline age of the granite was obtained from monazite U-Pb dating, and the source of the granite was determined using Li-Nd isotopes. The Madi rare metal granite is a high-K (calc-alkaline), peraluminous, S-type granite. The U-Pb monazite age indicates that the crystalline age of the granite is 175.6 Ma, which is Early Jurassic. The granite is characterized by a relatively wide range of δ7Li values (+2.99‰ to +5.83‰) and high lithium concentrations (181 ppm to 1022 ppm). The lithium isotopic composition of the granite does not significantly correlate with the degree of magmatic differentiation. An insignificant amount of lithium isotope fractionation occurred during the granitic differentiation. The lithium isotopic composition of the granite significantly differs from that of the wall rock, but it is very similar to that of a primitive mantle peridotite xenolith (mean δ7Li value +3.5‰). The plot of Li concentration versus δ7Li indicates that the Li isotopic composition of the granite is similar to that of island arc lavas. Based on the above-described evidence, the granite was mainly derived from the crust, but it was contaminated by a deep granitic magma.     

Characterization of C‐isotope variability in the Delhi Supergroup,northwestern India and the Mesoproterozoic ocean

Marine carbonate rocks of the Delhi Supergroup of northwestern India show little deviation in whole‐rock δ ¹³Ccarb and δ ¹⁸Ocarb values, which generally are around 0 and –10‰ respectively. These narrow ranges and almost constant δ ¹³Ccarb values persist despite close sampling through long sections. The data suggest that the global rate of organic carbon burial was probably constant during deposition of the Delhi Supergroup. The nearly invariant C isotopic profile of the Delhi Supergroup is similar to C isotopic profiles of Mesoproterozoic carbonates older than 1.3 Ga, as reported from different parts of world. Carbonate units on the western margin of the Delhi Supergroup however, have on average moderately positive δ ¹³C values (from 2 to +4.96‰). These high δ ¹³C carbonates may represent the Mesoproterozoic–Neoproterozoic transition (from ～1.25 to ～0.85 Ga), a period characterized by high positive δ ¹³C values globally.     

Bulk stable light isotopic ratios in archaeological birch bark tars

The authors report a preliminary study of the light stable isotopic (δD, δ¹³C and δ¹⁸O) values for bulk archaeological birch bark tars, over a geographical (e.g. Greece to Norway) and chronological (9500–3000 BP) range. For δ¹³C an increase in fractionation with increase in latitude is observed in samples from Greece which are less depleted than those from northern Europe. There is no clear difference between the samples from northern Europe. There is no apparent trend in δ¹³C value with the ¹⁴C age of the sample. Due to biosynthetic fractionation all the samples are significantly depleted in ²H and enriched in ¹⁸O relative to the global meteoric water line. This study indicates that archaeological birch bark tar from Greece can be distinguished from those of northern Europe; this separation is probably based on the extreme geographical range of the samples examined here. But this does provide evidence that the birch bark tars were probably made locally rather than traded.     

Carbon and oxygen isotope study of the active water-carbonate system in a karstic Mediterranean cave: Implications for paleoclimate research in semiarid regions

In a semiarid climatic zone, such as the Eastern Mediterranean region, annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave. Consequently, the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies. This is confirmed by a four-year study of the active carbonate-water system in the Soreq cave (Israel). The δ¹⁸O (SMOW) values of cave waters range from −6.3 to −3.5%.. The highest δ¹⁸O values occur at the end of the dry season in waters dripping from stalactites, and reflect evaporation processes in the epikarst zone, whereas the lowest values occur in rapidly dripping (fast-drip) waters at the peak of the rainy seasons. However, even fast-drip waters are about 1.5%. heavier than the rainfall above the cave, which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone. δ¹³C (PDB) values of dissolved inorganic carbon (DIC) vary from −15.6 to −5.4%., with fast-drip waters having lower δ¹³C values (mostly −15.6 to −12%.) and higher DIC concentrations relative to pool and stalactite-drip water. The low δ¹³C values of fast-drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil-CO₂ derived from overlying C₃-type vegetation and marine dolomite host rock.The δ¹⁸O (PDB) values of various types of present-day low-magnesium calcite (LMC) speleothems range from −6.5 to −4.3%. and δ¹³C values from −13 to −5.5%. and are not correlated with speleothem type. An analysis of δ¹⁸O values of present-day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium. Similarly, the measured ranges of δ¹³C and δ¹⁸O values for all types of present-day speleothems are consistent with equilibrium deposition at cave temperatures. The δ¹³C–δ¹⁸O range of contemporary LMC thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters. The 10%. variation in the δ¹³C values in waters can be modeled by a simple Rayleigh calculation of the carbon isotope fractionation accompanying CO₂-degassing and carbonate precipitation. These variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from C₃ to C₄-type plants. This consideration emphasizes that it is necessary to characterize the full range of δ¹³C values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types.Isotopic studies of a number of different types of fossil LMC speleothems show many of them to exhibit isotopic trends that are similar to those of present-day LMC, but others show both higher and lower δ¹⁸O ranges. In particular, the higher δ¹⁸O range has been shown by independent age-measurements to be associated with a period of drier conditions. The results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the δ¹⁸O–δ¹³C range representative of any given climatic period.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.