Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.     

Regional atmospheric circulation change in the North Pacific during the Holocene inferred from lacustrine carbonate oxygen isotopes, Yukon Territory, Canada

Analyses of sediment cores from Jellybean Lake, a small, evaporation-insensitive groundwater-fed lake, provide a record of changes in North Pacific atmospheric circulation for the last ∼7500 yr at 5- to 30-yr resolution. Isotope hydrology data from the southern Yukon indicate that the oxygen isotope composition of water from Jellybean Lake reflects the composition of mean-annual precipitation, δ¹⁸O_p. Recent changes in the δ¹⁸O of Jellybean sedimentary calcite (δ¹⁸O_ca) correspond to changes in the North Pacific Index (NPI), a measure of the intensity and position of the Aleutian Low (AL) pressure system. This suggests that δ¹⁸O_p variability was related to the degree of fractionation during moisture transport from the Gulf of Alaska across the St. Elias Mountains and that Holocene shifts were controlled by the intensity and position of the AL. Following this model, between ∼7500 and 4500 cal yr B.P., long-term trends suggest a predominantly weaker and/or westward AL. Between ∼4500 and 3000 cal yr B.P. the AL shifted eastward or intensified before shifting westward or weakening between ∼3000 and 2000 cal yr B.P. Rapid shifts eastward and/or intensification occurred ∼1200 and 300 cal yr B.P. Holocene changes in North Pacific atmospheric circulation inferred from Jellybean Lake oxygen isotopes correspond with late Holocene glacial advances in the St. Elias Mountains, changes in North Pacific salmon abundance, and shifts in atmospheric circulation over the Beaufort Sea.     

Climate deterioration in the Eastern Mediterranean as revealed by ion microprobe analysis of a speleothem that grew from 2.2 to 0.9 ka in Soreq Cave, Israel

Analysis of oxygen isotope ratios (δ¹⁸O) by ion microprobe resolves a sub-annual climate record for the Eastern Mediterranean from a Soreq Cave stalagmite that grew between 2.2 and 0.9 ka. In contrast to conventional drill-sampling methods that yield a total variation of 1.0‰ in δ¹⁸O_calcite values across our sample, the methods described here reveal up to 2.15‰ variation within single annual growth bands. Values of δ¹⁸O measured by ion microprobe vary in a regular saw-tooth pattern that correlates with annual, fluorescent growth banding where calcite grades from light to dark fluorescence. Modern records of precipitation and of cave dripwater indicate that variable δ¹⁸O_calcite values record regular seasonal differences in δ¹⁸O_rainfall modified by mixing in the vadose zone. Large differences in δ¹⁸O values measured across a single band (i.e., between the dark and light fluorescent calcite, or Δ¹⁸O_dark-light) are interpreted to indicate wetter years, while smaller differences represent drier years. Oxygen isotopes record: 1) month-scale growth increments, 2) changes in Δ¹⁸O_dark-light that represent seasonality, 3) a systematic, long-term decrease in maximum Δ¹⁸O_dark-light values, and 4) an overall increase in average δ¹⁸O_calcite values through time. These results suggest a drying of regional climate that coincides with the decline of the Roman and Byzantine Empires in the Levant region.     

N/N and O/O stable isotope ratios of nitrous oxide produced during denitrification in temperate forest soils

Anaerobic incubations of upland and wetland temperate forest soils from the same watershed were conducted under different moisture and temperature conditions. Rates of nitrous oxide (N₂O) production by denitrification of nitrate () and the stable isotopic composition of the N₂O (δ¹⁵N, δ¹⁸O) were measured. In all soils, N₂O production increased with elevated temperature and soil moisture. At each temperature and moisture level, the rate of N₂O production in the wetland soil was greater than in the upland soil. The ¹⁵N isotope effect (ε) _{(product − substrate)} ranged from −20‰ to −29‰. These results are consistent with other published estimates of ¹⁵N fractionation from both single species culture experiments and soil incubation studies from different ecosystems.A series of incubations were conducted with ¹⁸O-enriched water (H₂O) to determine if significant oxygen exchange (O-exchange) occurred between H₂O and N₂O precursors during denitrification. The exchange of H₂O-O with nitrite () and/or nitric oxide (NO) oxygen has been documented in single organism culture studies but has not been demonstrated in soils prior to this study. The fraction of N₂O-O derived from H₂O-O was confined to a strikingly narrow range that differed between soil types. H₂O-O incorporation into N₂O produced from upland and wetland soils was 86% to 94% and 64% to 70%, respectively. Neither the temperature, soil moisture, nor the rate of N₂O production influenced the magnitude of O-exchange. With the exception of one treatment, the net ¹⁸O isotope effect (ε_net) _{(product-substrate)} ranged from +37‰ to +43‰.Most previous studies that have reported ¹⁸O isotope effects for denitrification of to N₂O have failed to account for the effect of oxygen exchange with H₂O. When high amounts of O-exchange occur after fractionation during reductive O-loss, the ¹⁸O-enrichment is effectively lost or diminished and δ¹⁸O-N₂O values will be largely dictated by δ¹⁸O-H₂O values and subsequent fractionation. The process and extent of O-exchange, combined with the magnitude of oxygen isotope fractionation at each reduction step, appear to be the dominant controls on the observed oxygen isotope effect. In these experiments, significant oxygen isotope fractionation was observed to occur after the majority of water O-exchange. Due to the importance of O-exchange, the net oxygen isotope effect for N₂O production in soils can only be determined using δ¹⁸O-H₂O addition experiments with δ¹⁸O-H₂O close to natural abundance.The results of this study support the continued use of δ¹⁵N-N₂O analysis to fingerprint N₂O produced from the denitrification of . The utilization of ¹⁸O/¹⁶O ratios of N₂O to study N₂O production pathways in soil environments is complicated by oxygen exchange with water, which is not usually quantified in field studies. The oxygen isotope fractionation observed in this study was confined to a narrow range, and there was a clear difference in water O-exchange between soil types regardless of temperature, soil moisture, and N₂O production rate. This suggests that ¹⁸O/¹⁶O ratios of N₂O may be useful in characterizing the actively denitrifying microbial community.     

A model for oxygen and sulfur isotope fractionation in sulfate during bacterial sulfate reduction processes

We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns. Moreover, we show that a “typical” δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} slope does not exist. We postulate that measurements of δ³⁴S_{SO4_residual} and δ¹⁸O_{SO4_residual} can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ¹⁵N_{NO3_residual}, δ¹⁸O_{NO3_residual}, and the amount of residual nitrate during denitrification.     

Late Holocene inter-annual temperature variability reconstructed from the δ18O of archaeological Ostrea angasi shells

Two multi-year oxygen isotope (δ¹⁸O) records were obtained from archaeological Ostrea angasi shells, confirming the potential of this species to provide valuable environmental records for the late Holocene period in southeastern Australia. High-resolution δ¹⁸O_shell samples from the O. angasi clearly display a seasonal variability, offering insight into past climate conditions in a region where such information is presently limited.

The oxygen isotope record in O. angasi reflects a combined temperature–salinity signal. Observations of δ¹⁸O_shell data from modern specimens are used as a point of reference to assist in decoupling these two influences, with the two archaeological samples compared with the δ¹⁸O_shell profile of four modern O. angasi. Assuming similar paleo- δ¹⁸O_water values at the collection sites, data from these archaeological shells present a record of temperatures during the period of their growth that are consistently lower than modern day, with mean annual temperatures ～2°C cooler.     

黄土高原西部石笋记录的H2事件特征

青藏高原与黄土高原过渡带的甘肃武都万象洞位于现代夏季风的边缘区, 对气候变化极为敏感.通过洞内一支石笋WX40D的6个高精度TIMS-U系定年数据和616个样品的氧同位素测定, 建立了28.3~23.0 ka B.P., 分辨率约为10年的亚洲季风气候变化序列. 石笋δ18O记录揭示Marine Isotope Stage 2 (MIS2)早期东亚季风气候具有10~100 a尺度高频震荡特征, 从中识别出北大西洋Heinrich 2 (H2)特强冷事件, 且记录显示该事件开始于24.6 ka B.P., 呈突发式降温之后持续跌宕式降温变化. 对比研究发现, 万象洞石笋δ18O记录H2事件与葫芦洞、天鹅洞的石笋记录有差别, 但是与湖南金滩湾洞穴石笋δ18O记录、33°N太阳辐射强度以及极地GRIP冰心记录变化趋势一致, 表明季风边缘区气候变化主要受北半球中纬度太阳辐射能背景、北大西洋冰漂碎屑带的扩张以及低纬太平洋海表温度变化等因素的控制, 同时万象洞特殊的地理位置使得区域气候更易受到与极地气候有密切联系的亚洲冬季风和西风环流变化的影响.      

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.     

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

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

A bi-polar signal recorded in the western tropical Pacific: Northern and Southern Hemisphere climate records from the Pacific warm pool during the last Ice Age

Western tropical Pacific sea surface temperatures and Pacific Deep Water temperatures during Marine Isotope Stage 3 have been reconstructed from the δ¹⁸O and Mg/Ca of planktonic and benthic foraminifera from Marion Dufresne core MD98-2181. This 36 m marine core was collected at 6.3°N from a water depth of 2114 m. With sediment accumulation rates of up to 80 cm/ky, it provides a decadally resolved history of ocean variability during the Last Glacial period. Surface temperatures and salinities at this site varied in close association with millennial-scale atmospheric temperature swings at high northern latitudes as reflected in the GISP2 ice core. At times of colder atmospheric temperatures over Greenland, the western Pacific was more saline and summer season SSTs were ～2 °C colder. These millennial-scale changes within the tropics are attributed to a southward displacement of the summer season ITCZ in response to steeper meridional temperature gradients within the Pacific. The benthic δ¹⁸O record from MD98-2181 documents upper Pacific Deep Water temperature and salinity variability. Benthic δ¹⁸O variations of 0.3–0.5‰ during MIS 3 indicate deep waters within the Pacific were varying by ～1–1.5 °C, with the possibility that some of the variability was due to changing salinity and minor glacial–eustatic changes. The observed deep-water variability correlates to changes in Antarctic surface temperatures and thus reflects changes in Southern Ocean temperatures at the site of Pacific Deep Water formation. The combined planktonic and benthic records from MD98-2181 thus provide a northern and southern hemispheric climate record of anti-phased variability during MIS 3 as has been inferred previously from ice core records. Furthermore, the deep sea temperature excursions appear to have led millennial variations in atmospheric CO₂ as recorded in the EDML ice core by ～1 kyr.     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.     

Lake carbonate-δ18O records from the Yukon Territory,Canada: Little Ice Age moisture variability and patterns

A 1000-yr history of climate change in the central Yukon Territory, Canada, is inferred from sediment composition and isotope geochemistry from small, groundwater fed, Seven Mile Lake. Recent observations of lake-water δ¹⁸O, lake level, river discharge, and climate variations, suggest that changes in regional effective moisture (precipitation minus evaporation) are reflected by the lake’s hydrologic balance. The observations indicate that the lake is currently ¹⁸O-enriched by summer evaporation and that during years of increased precipitation, when groundwater inflow rates to the lake increase, lake-water δ¹⁸O values decrease. Past lake-water δ¹⁸O values are inferred from oxygen isotope ratios of fine-grained sedimentary endogenic carbonate. Variations in carbonate δ¹⁸O, supplemented by those in carbonate and organic δ¹³C, C/N ratios, and organic carbon, carbonate and biogenic silica accumulation rates, document changes in effective moisture at decadal time scales during the early Little Ice Age period to present. Results indicate that between ～AD 1000 and 1600, effective moisture was higher than today. A shift to more arid climate conditions occurred after ～AD 1650. The 19th and 20th centuries have been the driest of the past millennium. Temporal variations correspond with inferred shifts in summer evaporation from Marcella Lake δ¹⁸O, a similarly small, stratified, alkaline lake located ～250 km to the southwest, suggesting that the combined reconstructions accurately document the regional paleoclimate of the east-central interior. Comparison with regional glacial activity suggests differing regional moisture patterns during early and late Little Ice Age advances.     

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Modelling of the oxygen isotope evolution of seawater: implications for the climate interpretation of the δ18O of marine sediments

It is often argued that the δ¹⁸O value of oceanic water was maintained close to 0‰ for hundreds of millions of years, as a consequence of oxygen isotope exchange between oceanic crust and seawater. However, for several decades, the interpretation of the biosedimentary oxygen isotope record has conflicted with the igneous record because, with increasing age, a general trend of decreasing δ¹⁸O values (about 6‰) is observed in most carbonates, cherts and phosphates, especially for the Paleozoic and early Mesozoic. We developed a dynamical model of seawater-crust interaction that computes the δ¹⁸O value in these two reservoirs as function of time. This model takes into account the continuous production of crust at oceanic ridges, its expansion rate, the permeability profile with space and time, the mineralogical mode of the crust, and the kinetics of oxygen isotope exchange between rock-forming minerals and seawater. The model indicates that the δ¹⁸O value of seawater may vary by ±2‰ with a time response ranging from 5 to 50 Ma for expansion rates of 1 to 10 cm.a⁻¹. The variation of ±2‰ is fixed by both integrated water-rock ratio and closure time of the seawater-crust system by sediments. Variations in the oxygen isotope ratio of seawater through time have important implications for the interpretation of the systematically low δ¹⁸O values of pre-Jurassic marine sediments. According to our model, marine paleotemperatures could be up to 10°C lower than those expected when applying the classical hypothesis of an ice-free ocean with a δ¹⁸O value of −1‰.     

Natürliche Isotopengehalte von Nitrat als Indikatoren für dessen Herkunft

The δ¹⁵N-value has often tentatively been used for the assignment of nitrate to its origin. However, the very complex correlations between the different nitrogen pools, mostly accompanied by isotope discriminations, oppose a very limited application of this method. On the other hand, the oxygen isotope abundance should be more indicative, because industrially produced NO⁻₃ must nearly exclusively contain oxygen from O₂ (δ¹⁸O = +23.5%.), while NO⁻₃ originating from a nitrification process must have water (δ¹⁸O ≅ -10%.) as the main oxygen source.For the proof of this reflection a method for the precise oxygen isotope analysis of NO⁻₃ was developed. Its application to the δ-value determination of commercial fertilizers and NO⁻₃ formed by nitrification absolutely confirmed the above predictions. Similarly, the isotope abundance of NO⁻₃-samples from ground and drinking water of known origin corresponded to the expected values. On the basis of these results and taking into account the known isotope abundance shifts due to isotope effects of nitrification and denitrification, a diagram between δ¹⁵N- and δ¹⁸O-values for NO⁻₃ was developed, which permitted the assignment of NO⁻₃ in unknown water samples to its probable source and origin.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Quartz Reference Materials for Oxygen Isotope Analysis by SIMS

Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ¹⁸O values were determined by CO₂ laser fluorination. The average δ¹⁸O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.     

Seasonal variability of oxygen and hydrogen stable isotopes in precipitation and cave drip water at Guilin,southwest China

The interpretation of climatic information from stalagmites has traditionally been a complex research problem, with oxygen isotopes playing a particularly important role in global climate change studies. This study investigates the relationship between oxygen isotope composition of the atmospheric in precipitation and cave drip water at Panlong cave in southwest China on seasonal timescales of variability. Time series seasonal variability was derived from Panlong cave in Guilin by collecting daily precipitation samples for stable isotope analysis during 2012. Results indicate that δ¹⁸O of precipitation contains a clear seasonal variation whereby higher values are mainly distributed during winter and lower values during summer. Seasonal variations in water sources affect the precipitation δ¹⁸O values. Drip water δ¹⁸O also displayed a seasonal cycle which is attenuated relative to δ¹⁸O of precipitation. Drip water time series display seasonal cycle ranges from 1.5 to 3.5 ‰ relative to Vienna Standard Mean Ocean Water, which mainly follow the precipitation δ¹⁸O seasonal cycle. Seasonal variation in drip water δ¹⁸O supports interpretations of the stalagmite δ¹⁸O record as a paleoclimate proxy sensitive to the local environment. This monitoring experiment revealed that drip water must be transported through the epikarst in approximately 1.5 months during cold periods, and <0.5 months during warm periods. Different residence time percolation is mainly affected by the atmospheric precipitation amount, depending on whether soil moisture reaches saturation.     

Sea-land oxygen isotopic relationships from planktonic foraminifera and speleothems in the Eastern Mediterranean region and their implication for paleorainfall during interglacial intervals

The oxygen and carbon stable isotope compositions of cave speleothems provide a powerful method for understanding continental climate change. Here, we examine the question of the regionality of this isotopic record and its linkage with the marine isotopic record in the Eastern Mediterranean (EM) region. The study presents a new, accurately dated 250-kyr δ¹⁸O and δ¹³C record determined from speleothems of the Peqiin Cave, Northern Israel. Its comparison with the continuous 185-kyr isotopic record of the Soreq Cave speleothems from Central Israel reveals striking similarities. Thus, a strong regional climatic signal, brought about by variations in temperature and rainfall amount, is reflected in both cave records. Low δ¹⁸O minima in the Peqiin profile for the last 250- to 185-kyr period (interglacial marine isotopic stage 7) match the timing of sapropels 9 to 7 and are indicative of high rainfall in the EM region at these times. The combined Soreq and Peqiin δ¹⁸O record for the last 250 kyr excellently matches the published Globigerinoides ruber (G. ruber) marine δ¹⁸O record for the EM Sea, with the isotopic compositional difference Δ_{G.ruber-speleothems} remaining relatively constant at −5.6 ± 0.7‰, thus establishing for the first time a robust, exploitable link between the land and the marine isotopic records. The correspondence of low δ¹⁸O speleothem values and high cave water stands with low G. ruber δ¹⁸O values during interglacial sapropel events indicates that these periods were characterized by enhanced rainfall in the EM land and sea regions. By use of sea surface temperatures derived from alkenone data as a proxy for land temperatures at the Soreq Cave, we calculate the paleorainfall δ¹⁸O values and its amounts. Maximum rainfall and lowest temperature conditions occurred at the beginning of the sapropel events and were followed by decrease in rainfall and increase in temperatures, leading to arid conditions. The record for the last 7000 yr shows a trend toward increasing aridity and agrees well with climatic and archeological data from North Africa and the Middle East.     

Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years

Sundqvist, H. S., Holmgren, K., Moberg, A., Spötl, C. & Mangini, A. 2009: Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years. Boreas, 10.1111/j.1502‐3885.2009.00099.x. ISSN 0300‐9483. This study of a 4000‐year‐old stalagmite from Korallgrottan in northwestern Sweden highlights the potentials and challenges when using stable isotopes in stalagmites as climate proxies, as well as the fact that the relationship between climate and proxy may change through time. Both the oxygen and the carbon isotopes display an overall trend of enrichment together with decreasing growth rates over the time period covered by the stalagmite, which is considered a generally cooling period according to current palaeoclimate understanding. The stable isotope records show enriched isotopic values during the, for Scandinavia, comparatively cold period AD 1300–1700 and depleted values during the warmer period AD 800–1000. The indication of a negative relationship between measured δ¹⁸O and surface temperature concurs with earlier reported stalagmite records from regions with a seasonal snow cover and is further supported by the fact that the stalagmite δ¹⁸O record shows general similarities with both regional and hemispheric temperature reconstructions available for the past 500 and 2000 years, respectively. Compared with a stable isotope record of lacustrine carbonates from northern Sweden, however, shifting correlations over time between the two records indicate that a local hydrological change may have taken place at Korallgrottan, or at the lake, compared with around 1000 years ago. The earlier part of the stalagmite δ¹⁸O might thus be influenced, to some extent, by another process than the later part, which means that a negative relationship between δ¹⁸O and surface temperature might not hold for the entire 4000‐year‐old record.