Isotope variations in a Sierra Nevada snowpack and their relation to meltwater

Isotopic variations in melting snow are poorly understood. We made weekly measurements at the Central Sierra Snow Laboratory, California, of snow temperature, density, water equivalent and liquid water volume to examine how physical changes within the snowpack govern meltwater δ¹⁸O. Snowpack samples were extracted at 0.1 m intervals from ground level to the top of the snowpack profile between December 1991 and April 1992. Approximately 800 mm of precipitation fell during the study period with δ¹⁸O values between −21.35 and −4.25‰. Corresponding snowpack δ¹⁸O ranged from −22.25 to −6.25‰. The coefficient of variation of δ¹⁸O in snowpack levels decreased from −0.37 to −0.07 from winter to spring, indicating isotopic snowpack homogenization. Meltwater δ¹⁸O ranged from −15.30 to −8.05‰, with variations of up to 2.95‰ observed within a single snowmelt episode, highlighting the need for frequent sampling. Early snowmelt originated in the lower snowpack with higher δ¹⁸O through ground heat flux and rainfall. After the snowpack became isothermal, infiltrating snowmelt displaced the higher δ¹⁸O liquid in the lower snowpack through a piston flow process. Fractionation analysis using a two-component mixing model on the isothermal snowpack indicated that δ¹⁸O in the initial and final half of major snowmelt was 1.30‰ lower and 1.45‰ higher, respectively, than the value from simple mixing. Mean snowpack δ¹⁸O on individual profiling days showed a steady increase from −15.15 to −12.05‰ due to removal of lower δ¹⁸O snowmelt and addition of higher δ¹⁸O rainfall. Results suggest that direct sampling of snowmelt and snow cores should be undertaken to quantify tracer input compositions adequately. The snowmelt sequence also suggests that regimes of early lower δ¹⁸O and later higher δ¹⁸O melt may be modeled and used in catchment tracing studies.     

Late Pleistocene to Holocene composite speleothem O and C chronologies from South Island, New Zealand—did a global Younger Dryas really exist?

Oxygen and carbon data from eight stalagmites from northwest South Island are combined to produce composite records of δ¹⁸O and δ¹³C from 23.4 ka to the present. The chronology is anchored by 43 thermal ionization mass spectrometry (TIMS) uranium series ages. Delta ¹⁸O values are interpreted as having a first order positive relationship to temperature, but also to be influenced by precipitation in a complex manner. Delta ¹³C is interpreted as responding negatively to increases in atmospheric CO₂ concentration, biological activity and precipitation amount.

Six climatic phases are recognized. After adjustment of 1.2‰ for the ice volume effect, the δ¹⁸O record between 23 and 18 ka varies around −3.72‰ compared to the Holocene average of −3.17‰. Late-glacial warming commenced between 18.2 and 17.8 ka and accelerated after 16.7 ka, culminating in a positive excursion between 14.70 and 13.53 ka. This was followed by a significant negative excursion between 13.53 and 11.14 ka of up to 0.55‰ depth that overlapped the Antarctic Cold Reversal (ACR) and spanned the Younger Dryas (YD). Positive δ¹⁸O excursions at 11.14 ka and 6.91–6.47 ka represent the warmest parts of the Holocene. The mid-Holocene from 6 to 2 ka was marked by negative excursions that coincide with increased glacial activity in the South Island. A short positive excursion from 0.71 to 0.57 ka was slightly later than the Medieval Warm Period of Europe.

Delta ¹³C values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in δ-values after 17.79 ka probably corresponds to an increase in atmospheric CO₂ concentration, biological activity and wetness at the end of the Last Glaciation, but the reversal identified in the δ¹⁸O record from 13.53 to 11.14 ka was not reflected in δ¹³C changes. The lowest δ¹³C values coincided with the early Holocene climatic suboptimum when conditions were relatively wet as well as mild.

Major trends in the δ¹⁸O_c record are similar to the Northern Hemisphere, but second order detail is often distinctly different. Consequently, at the millennial scale, a more convincing case can be made for asymmetric climatic response between the two hemispheres rather than synchronicity.     

Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations

The stable isotopic composition of hydrogen and oxygen (δ²H and δ¹⁸O) and tritium activity (³H) were monitored in monthly precipitation at two continental stations (Ljubljana, Zagreb) and six stations along the eastern Adriatic coasts of Slovenia and Croatia in the period 2001–2003. Mean air temperatures and amount of precipitation were also recorded.

Distinct differences in both meteorological and isotopic data between the continental and maritime stations were observed. Seasonal variations in δ¹⁸O are smaller at the maritime stations than at the continental ones due to smaller seasonal temperature variations. A good correlation between δ¹⁸O and δ²H was obtained for each station, and the local meteoric water lines are close to the Global Meteoric Water Line, with a decreasing trend of slope for the south-Adriatic stations. Good correlations between δ¹⁸O in monthly precipitation and mean monthly air temperature were observed at all stations. The slope of δ¹⁸O vs. T varied between 0.37‰ °C⁻¹ and 0.15‰ °C⁻¹. Mean ³H activity and seasonal variation of ³H activity are smaller at maritime stations than at continental ones. Additionally, ³H activity decreases in the NW–SE direction of the Adriatic coast.

The study of spatial variations over this relatively small area rich in geographical and climatic diversities showed the complexity of the isotopic composition of precipitation and the isotopic data obtained for eight stations, most of them in the karstic area along the Adriatic coast, and gave valuable information for regional hydrological investigations and modelling of isotope variability over the Mediterranean basin.     

Stable isotope values of Costa Rican surface waters

Stable isotope data of surface waters from the humid tropics in general, and Costa Rica in particular, are scarce. To improve our understanding of the spatial distribution of stable isotopes in surface waters, we measured δ¹⁸O and δD in river and lake (n=63) and precipitation (n=3) samples from Costa Rica. We also present data from the IAEA/WMO isotopes in precipitation network as context for our study. Surface water isotope values do not strongly correlate with elevation, stream head elevation, stream length, distance from Caribbean Sea, or estimated mean annual precipitation for the country as a whole. However, the data show distinct regional trends. The δ¹⁸O and δD values downwind of mountain ranges are inversely related to the altitude of the ranges the air masses traverse. In the lee of the high Talamanca Range, δ¹⁸O values are 6–8‰ lower, while in the lee of the lower Tilarán Range δ¹⁸O values are 2–3‰ lower than upwind sites along the Caribbean Slope. An altitude effect of −1.4‰ δ¹⁸O/km is present on the Pacific slope of southern Costa Rica, equivalent to a temperature effect of −0.3‰/°C. The Nicoya and Osa Peninsulas have higher values than upwind sites, suggesting input of Pacific-sourced moisture, evaporative enrichment, or decreased condensation temperatures. Elevated and increasing d-excess values inland along the Nicaragua Trough suggest a recycled component may be an important contributor to the water budget. These data provide preliminary stable isotope information for Costa Rica, and will benefit paleoclimatic research in the region. More detailed studies would be beneficial to our understanding of the controls on stable isotope composition of tropical waters.     

Preliminary stratigraphic and structural architecture of Bhutan: Implications for the along strike architecture of the Himalayan system

High-precision in-situ ion microprobe (SIMS) oxygen isotope analysis of zircons from two diorite intrusions associated with the late Caledonian Lochnagar pluton in Scotland has revealed large differences in the degree of heterogeneity in zircon δ¹⁸O between the diorites. Zircon crystals from the Cul nan Gad diorite (CnG) show a unimodal distribution of oxygen isotope values (δ¹⁸O = 6.0 ± 0.6‰ (2σ)) and no or only minor grain-scale variation. Those from the Allt Darrarie diorite (AD1) show a large range in δ¹⁸O and an apparent bimodal distribution with modes of 6.6 ± 0.4‰ and 7.3 ± 0.4‰. Variations of up to 1.2‰ occur between and within grains; both an increase and decrease in δ¹⁸O with zircon growth has been observed. The δ¹⁸O composition of growing zircon can only change if open-system processes affect the magma composition, i.e. if material of contrasting δ¹⁸O composition is added to the magma. The variability in AD1 is interpreted to represent a cryptic record of magma mixing. A ‘deep crustal hot zone’ is a likely site for generation of the dioritic magmas which developed by mixing of residual melts and crustal partial melts or by melting of mafic lower crustal rocks. The overall small number of zircons with mantle-like δ¹⁸O values (5.3 ± 0.6‰ (2σ)) in the Lochnagar diorites is largely the product of crustal differentiation rather than crustal growth.

The δ¹⁸O of quartz from the CnG and AD1 diorites shows only minor variation (CnG: 10.9 ± 0.5‰ (2σ), AD1: 11.7 ± 0.6‰ (2σ)) within single populations, with no evidence of mixing. Quartz–zircon isotopic disequilibrium is consistent with later crystallisation of quartz from late magmatic fluids, and in case of the AD1 diorite after the inferred magma mixing from a homogenised, higher δ¹⁸O melt.

High-precision SIMS oxygen isotope analysis of zircon provides a new approach to identifying and resolving previously undetected early-stage magma mixing and constraining the compositions and origins of the component magmas. A combination of zircon, quartz and whole-rock data has proven to be a powerful tool in reconstructing the petrogenetic evolution of diorite from early crystallisation to late alteration.     

Can biomass burning produce a globally significant carbon-isotope excursion in the sedimentary record?

Negative carbon-isotope excursions have been comprehensively studied in the stratigraphic record but the discussion of causal mechanisms has largely overlooked the potential role of biomass burning. The carbon-isotopic ratios (δ¹³C) of vegetation, soil organic matter and peat are significantly lower than atmospheric carbon dioxide (CO₂), and thereby provide a source of low ¹³C CO₂ when combusted. In this study, the potential role of biomass burning to generate negative carbon isotope excursions associated with greenhouse climates is modeled. Results indicate that major peat combustion sustained for 1000 yr increases atmospheric CO₂ from 2.5× present atmospheric levels (PAL) to 4.6× PAL, and yields a pronounced negative δ¹³C excursion in the atmosphere ( 2.4‰), vegetation ( 2.4‰) and the surface ocean ( 1.2‰), but not for the deep ocean ( 0.9‰). Release of CO₂ initiates a short-term warming of the atmosphere (up to 14.4 °C, with a duration of 1628 yr), which is consistent with the magnitude and length of an observed Toarcian excursion event. These results indicate that peat combustion is a plausible mechanism for driving negative δ¹³C excursions in the rock record, even during times of elevated pCO₂.     

Bomb C time history recorded in two modern stalagmites — importance for soil organic matter dynamics and bomb C distribution over continents

Carbon 14 activity measurements made by Accelerator Mass Spectrometry on two modern stalagmites from the Han-sur-Lesse cave (Belgium) and from the Postojna Cave (Slovenia) permit the construction of ¹⁴C activity (a¹⁴C) time series over the last 50 years. A high precision chronology is given by annual laminae in the first stalagmite and by a specific mark (explosion in the Postojna Cave in 1944) in the second one. In both stalagmites, ¹⁴C activity increase due to nuclear tests in the atmosphere is remarkable. However, instead of a sharp peak like the one observed in the atmosphere around 1963–1964, the ¹⁴C activities of the stalagmite CaCO₃ show an abrupt increase, with an offset of 1–10 years, followed by a high activity plateau for the Han-sur-Lesse sample and a slight decrease for the Postojna sample. For both stalagmites, the variation of the a¹⁴C amplitude between pre- and post-bomb period is much lower than the atmospheric record, which demonstrates the damping effect of the soil carbon reservoir. We have modeled the CaCO₃ activities using fractionation processes between atmosphere CO₂, soil CO₂ and organic matter (OM), dissolved inorganic carbon and stalagmite CaCO₃. In both cases studied, the model and former soil studies suggest that CO₂ from soil organic matter (SOM) decomposition, which has a slow turnover (i.e. >1 y), is of major importance in winter, when the development of speleothem is the most important. Combined with the fact that 80–90% of the stalagmite carbon comes from soil CO₂, this produces a damping effect on the speleothem a¹⁴C. Consequently, the ‘geochemical time resolution', at least for speleothem carbon, is much lower than the structural resolution given by annual laminae alternations and is mainly controlled by soil carbon dynamics: a¹⁴C and δ¹³C are smoothed over several years. Differences between the ¹⁴C time series of the Han-sur-Lesse and Postojna stalagmites are likely to be due to the double amount of precipitation in Postojna, which produces a faster soil OM turnover and thus a ‘system' which is more sensitive to atmospheric changes.     

Deduction of groundwater flow regime in a basaltic aquifer using geochemical and isotopic data: The Golan Heights, Israel case study

Groundwater flow-paths through shallow-perch and deep-regional basaltic aquifers at the Golan Heights, Israel, are reconstructed by using groundwater chemical and isotopic compositions. Groundwater chemical composition, which changes gradually along flow-paths due to mineral dissolution and water–rock interaction, is used to distinguish between shallow-perched and deep-regional aquifers. Groundwater replenishment areas of several springs are identified based on the regional depletion in rainwater δ¹⁸O values as a function of elevation (−0.25‰ per 100 m). Tritium concentrations assist in distinguishing between pre-bomb and post-bomb recharged rainwater.

It was found that waters emerging through the larger springs are lower in δ¹⁸O than surrounding meteoric water and poor in tritium; thus, they are inferred to originate in high-elevation regions up to 20 km away from their discharge points and at least several decades ago. These results verify the numerically simulated groundwater flow field proposed in a previous study, which considered the geological configuration, water mass balance and hydraulic head spatial distribution.     

Using SPIRAL (Single Pollen Isotope Ratio AnaLysis) to estimate C3- and C4-grass abundance in the paleorecord

C₃ and C₄ grasses differ greatly in their responses to environmental controls and influences on biogeochemical processes (e.g. water, carbon, and nutrient cycling). Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. Stable carbon isotopic analysis of individual grains of grass pollen using a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer holds promise for improving C₃ and C₄ grass reconstructions. This technique, SPIRAL (Single Pollen Isotope Ratio AnaLysis), has only been evaluated using pollen of known C₃ and C₄ grasses. To test the ability of SPIRAL to reproduce the abundance of C₃ and C₄ grasses on the landscape, we measured δ¹³C values of > 1500 individual grains of grass pollen isolated from the surface sediments of ten lakes in areas that span a large gradient of C₃- and C₄-grass abundance, as determined from vegetation surveys. Results indicate a strong positive correlation between the δ¹³C-based estimates of % C₄-grass pollen and the abundance of C₄ grasses on the landscape. The % C₄-grass pollen slightly underestimates the actual abundance of C₄ grasses at sites with high proportions of C₄ grasses, which can be corrected using regression analysis. Comparison of the % C₄-grass pollen with C/N and δ¹³C measurements of bulk organic matter illustrates the distinct advantages of grass-pollen δ¹³C as a proxy for distinguishing C₃ and C₄ shifts within the grass family. Thus SPIRAL promises to advance our understanding of grassland ecology and evolution.     

Stable isotope evidence of dual (Arabian Sea and Bay of Bengal) vapour sources in monsoonal precipitation over north India

High resolution time series data of hydrogen (δD) and oxygen (δ¹⁸O) isotope values of precipitation have been generated for the first time at Kolkata, eastern India where the summer monsoon clouds from Bay of Bengal (BOB) commence their journey over India. Use of a Rayleigh cum two component mixing model and comparison of Kolkata data with the International Atomic Energy Agency (IAEA)–Global Network of Isotopes in Precipitation (GNIP) data base of New Delhi suggest that the precipitation at New Delhi cannot be explained by simple continental effect of a BOB vapour source alone, traveling and raining successively along Kolkata–New Delhi route. It is necessary to invoke an admixture of  20% vapour originating from the Arabian sea with the vapour coming from BOB and finally causing summer monsoon rains at New Delhi. The findings have major implications to the regional water vapour budget over India.     

Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys

Many of the heaviest and lightest natural zinc (Zn) isotope ratios have been discovered in hydrothermal ore deposits. However, the processes responsible for fractionating Zn isotopes in hydrothermal systems are poorly understood. In order to better assess the total range of Zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation, we have measured Zn isotopes in seafloor hydrothermal fluids from numerous vents at 9–10°N and 21°N on the East Pacific Rise (EPR), the TAG hydrothermal field on the Mid-Atlantic Ridge, and in the Guaymas Basin. Fluid δ⁶⁶Zn values measured at these sites range from + 0.00‰ to + 1.04‰. Of the many physical and chemical parameters examined, only temperature was found to correlate with fluid δ⁶⁶Zn values. Lower temperature fluids (< 250 °C) had both heavier and more variable δ⁶⁶Zn values compared to higher temperature fluids from the same hydrothermal fields. We suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite (Zn sulfide), and that this process is a primary cause of Zn isotope variation in hydrothermal fluids. Thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest Zn found in fluids that were calculated to be saturated with respect to sphalerite. We have also measured Zn isotopes in chimney sulfides recovered from a high-temperature (383 °C) and a low-temperature (203 °C) vent at 9–10°N on the EPR and, in both cases, found that the δ⁶⁶Zn of chimney minerals was lighter or similar to the fluid δ⁶⁶Zn. The first measurements of Zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid δ⁶⁶Zn, and suggest that subsurface Zn sulfide precipitation is a primary factor in causing variations in fluid δ⁶⁶Zn. By understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid δ⁶⁶Zn, Zn isotopes may be used as a tracer for studying hydrothermal processes.     

A stratigraphic network across the Subtropical Front in the central South Atlantic: Multi-parameter correlation of magnetic susceptibility, density, X-ray fluorescence and δO records

Computer aided multi-parameter signal correlation is used to develop a common high-precision age model for eight gravity cores from the subtropical and subantarctic South Atlantic. Since correlations between all pairs of multi-parameter sequences are used, and correlation errors between core pairs (A, B) and (B, C) are controlled by comparison with (A, C), the resulting age model is called a stratigraphic network. Precise inter-core correlation is achieved using high-resolution records of magnetic susceptibility κ, wet bulk density ρ and X-ray fluorescence scans of elemental composition. Additional δ¹⁸O records are available for two cores. The data indicate nearly undisturbed sediment series and the absence of significant hiatuses or turbidites. After establishing a high-precision common depth scale by synchronously correlating four densely measured parameters (Fe, Ca, κ, ρ), the final age model is obtained by simultaneously fitting the aligned δ¹⁸O and κ records of the stratigraphic network to orbitally tuned oxygen isotope [J. Imbrie, J. D. Hays, D. G. Martinson, A. McIntyre, A. C. Mix, J. J. Morley, N. G. Pisias, W. L. Prell, N. J. Shackleton, The orbital theory of Pleistocene climate: support from a revised chronology of the marine δ¹⁸O record, in: A. Berger, J. Imbrie, J. Hays, G. Kukla, B. Saltzman (Eds.), Milankovitch and Climate: Understanding the Response to Orbital Forcing, Reidel Publishing, Dordrecht, 1984, pp. 269-305; D. Martinson, N. Pisias, J. Hays, J. Imbrie, T. C. Moore Jr., N. Shackleton, Age dating and the orbital theory of the Ice Ages: development of a high-resolution 0 to 300.000-Year chronostratigraphy, Quat. Res. 27 (1987) 1-29.] or susceptibility stacks [T. von Dobeneck, F.Schmieder, Using rock magnetic proxy records for orbital tuning and extended time series analyses into the super-and sub-Milankovitch Bands, in: G. Fischer, G. Wefer (Eds.), Use of proxies in paleoceanography: Examples from the South Atlantic, Springer-Verlag, Berlin (1999), pp. 601-633.]. Besides the detection and elimination of errors in single records, the stratigraphic network approach allows to check the intrinsic consistency of the final result by comparing it to the outcome of more restricted alignment procedures. The final South Atlantic stratigraphic network covers the last 400 kyr south and the last 1200 kyr north of the Subtropical Front (STF) and provides a highly precise age model across the STF representing extremely different sedimentary regimes. This allows to detect temporal shifts of the STF by mapping δMn / Fe. It turns out that the apparent STF movements by about 200 km are not directly related to marine oxygen isotope stages.     

Oxygen isotope measurements of mammoth and reindeer skeletal remains: an archive of Late Pleistocene environmental conditions in Eurasian Arctic

58 samples of fossil mammoth and reindeer teeth and bones of various ages and coming from different locations were studied for the oxygen isotopic composition of their phosphate. Samples from Siberia have interstadial (Marine Isotope Stage 3), stadial (MIS 2), late-glacial and post-glacial ages. Russian and Ukrainian samples refer to the late-glacial and transitional (between the interstadial and glacial stages) time. The δ¹⁸O of palaeoenvironmental waters were calculated from the δ¹⁸O_p obtained from fossil samples by means of the isotope equations calibrated on modern specimens of elephants and deer respectively. The δ¹⁸O_w obtained are generally lighter than those measured nowadays in the same areas and not far from those measured on ice cores of Holocene age, the isotopic differences being not greater than a few δ units. The calculated values are also in fairly good agreement with some isotopic values obtained from Siberian permafrost samples. According to the results obtained it seems that the elephant and deer equations can be reasonably used respectively in the case of fossil mammoth and deer skeletons to evaluate environmental palaeowaters.     

Glacial–interglacial changes in Subantarctic sea surface temperature and δO-water using foraminiferal Mg

Laboratory culturing experiments with living Globigerina bulloides indicate that Mg/Ca is primarily a function of seawater temperature and suggest that Mg/Ca of fossil specimens is an effective paleotemperature proxy. Using culturing results and a core-top Neogloboquadrina pachyderma calibration, we have estimated glacial–interglacial changes in sea surface temperature (SST) using planktonic Mg/Ca records from core RC11-120 in the Subantarctic Indian Ocean (43°S, 80°E) and core E11-2 in the Subantarctic Pacific Ocean (56°S, 115°W). Our results suggest that glacial SST was about 4°C cooler in the Subantarctic Indian Ocean and 2.5°C cooler in the Subantarctic Pacific. Comparison of SST and planktonic δ¹⁸O records indicates that changes in SST lead changes in δ¹⁸O by on average 1–3 kyr. The glacial–interglacial temperature change indicated by the Subantarctic Mg/Ca records suggests that temperature accounts for 40–60% of the foraminiferal δ¹⁸O change. We have used the Mg/Ca-based SST estimates and δ¹⁸O determinations to generate site-specific seawater δ¹⁸O records, which suggest that seawater δ¹⁸O was on average 1‰ more positive during glacial episodes compared with interglacial episodes.     

Calibrations for benthic foraminiferal Mg/Ca paleothermometry and the carbonate ion hypothesis

Benthic foraminiferal magnesium/calcium ratios were determined on one hundred and forty core-top samples from the Atlantic Ocean, the Norwegian Sea, the Indian Ocean, the Arabian Sea and the Pacific Ocean, mostly at sites with bottom water temperatures below 5 °C. Mg/Ca ratios are consistently lower, by  0.2 mmol/mol, in samples cleaned using oxidative and reductive steps than using oxidative cleaning. Differences between Cibicidoides species have been identified: Mg/Ca of Cibicidoides robertsonianus > Cibicidoides kullenbergi > Cibicidoides wuellerstorfi. Comparison with bottom water temperatures support observations of lowered Mg/Ca of C. wuellerstorfi at temperature below  3 °C compared with values predicted by published calibrations and from other Cibicidoides species. Hydrographic data shows that carbonate ion saturation (Δ[CO₃²⁻]) decreases rapidly below this temperature. An empirical sensitivity of Δ[CO₃²⁻] on Mg/Ca has been established for C. wuellerstorfi of 0.0086 ± 0.0006 mmol/mol/μmol/kg. A novel application using modern temperatures and Last Glacial Maximum temperatures derived via pore fluid modelling supports a carbonate ion saturation state effect on Mg incorporation. This may significantly affect calculated δ¹⁸O_seawater obtained from foraminiferal δ¹⁸O and Mg/Ca temperature.     

Characteristics of water isotopes and hydrograph separation during the wet season in the Heishui River, China

Runoff generation and dynamics is an important issue in watershed and water resource management, but the mechanism in large scale is unclear and site-dependent. For this reason, spatial variations of δD and δ¹⁸O of river water and their sources within large-area of the Heishui Valley of the upper Yangtze River in western China were investigated during the wet season. A total 117 river water samples were collected at 13 sampling sites located at the junction of the principal river course and its tributaries. The results showed no spatial variations of either δD or δ¹⁸O values existed among tributary sampling sites A, B, E, F, H and I during the wet season, and significantly spatial variation occurred between tributary sampling sites A, B, E, F, H, I and site K; which indicated different proportions of rain entering river water should lead to spatial variation of water isotopes. The hydrograph separation analysis, based on the isotope data of river water, meltwater and rain water samples, showed the contribution of snow and glacier meltwater varied from 63.8% to 92.6%, and that of rain varied from 7.4% to 36.2%; which meant that snow and glacier meltwater was the main supplying water source of baseflow in the Heishui Valley. And the roles of glacier and snow meltwater should be significantly noticed in water resource management in this alpine valley at the rim of the Tibetan Plateau.     

Organic carbon and nitrogen stable isotopes in the intertidal sediments from the Yangtze Estuary, China

The natural isotopic compositions and C/N elemental ratios of sedimentary organic matter were determined in the intertidal flat of the Yangtze Estuary. The results showed that the ratios of carbon and nitrogen stable isotopes were respectively −29.8‰ to − 26.0‰ and 1.6‰–5.5‰ in the flood season (July), while they were −27.3‰ to − 25.6‰ and 1.7‰–7.8‰ in the dry season (February), respectively. The δ¹³C signatures were remarkably higher in July than in February, and gradually increased from the freshwater areas to the brackish areas. In contrast, there were relatively complex seasonal and spatial changes in stable nitrogen isotopes. It was also reflected that δ¹⁵N and C/N compositions had been obviously modified by organic matter diagenesis and biological processing, and could not be used to trace the sources of organic matter at the study area. In addition, it was considered that the mixing inputs of terrigenous and marine materials generally dominated sedimentary organic matter in the intertidal flat. The contribution of terrigenous inputs to sedimentary organic matter was roughly estimated according to the mixing balance model of stable carbon isotopes.     

Origin and age of thermal waters in Cieplice Spa, Sudeten, Poland, inferred from isotope, chemical and noble gas data

Isotope and hydrochemical data of the thermal water system in Cieplice laskie Zdrój (Spa) indicate the existence of two subsystems that greatly differ in volume and which meet at the fault zones of a granitic horst, where they discharge at an altitude of about 340m. One of the subsystems is very small (about 4 × 10³ m³) as indicated by the tritium age of the order of 10 years and a low outflow rate. Its recharge area found from the δ¹⁸O and δD values, is about 200m above the springs, most probably on the slopes of the foothills of the Karkonosze Mountains south-southwest of the spa. The large subsystem contains water which is free of tritium and whose ¹⁴C content is from 1 to 8 pmc with δ¹³C = −8.0 to −9.2‰. The isotopic composition of this water reflects either the climatic effect (low-altitude recharge during a cooler pre-Holocene climate) or the altitude effect (recharge in the early Holocene period at about 1000m at the heights of the Karkonosze assuming that the ¹⁴C concentration is strongly reduced by exchange with calcite in veins). For the former hypothesis, the recharge area of this water is probably either at the foot of the southeastern slopes of the Kaczawa Mountains or/and at the foot of the Rudawy Janowickie Mountains, to the east of Cieplice. The noble gas temperatures are more consistent with the pre-Holocene recharge. Similarly, the ⁴He excess and ⁴⁰Ar/³⁶Ar ratio support the hypothesis of a pre-Holecene age. The constant ³He/⁴He ratio of 26 × 10⁻⁸ for highly different helium contents indicates crustal origin of helium. For the pre-Holocene age of water its volume is calculated at >- 10⁹m³ (stagnant water in micropores and mobile water in fractures) and the hydraulic conductivity of the host granite massif is estimated at about 7 × 10⁻⁸ ms⁻¹. Two outflows from this subsystem have different and variable fractions of a modern water component (bomb age), most probably originating from the bank infiltration of a nearby stream.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Compound-specific radiocarbon dating of Ross Sea sediments: A prospect for constructing chronologies in high-latitude oceanic sediments

We present an overview of the problems relating to the development of sedimentary chronologies for Antarctic margin sediments, and review the recent application of compound-specific radiocarbon dating methods for resolving them. Radiocarbon dating of solvent-extractable, short-chain (C₁₄, C₁₆, and C₁₈) fatty acids isolated from surface sediments of the Ross Sea, Antarctica, revealed their ages to be consistent with that of the modern dissolved inorganic carbon (DIC) reservoir age (pre-bomb, Δ¹⁴C≈−150‰; post-bomb, Δ¹⁴C≈−100‰) in this region. This contrasts sharply with the radiocarbon ages of bulk organic matter in the corresponding sediments are substantially older (Δ¹⁴C=−298‰ to −712‰). Furthermore, the radiocarbon ages of these fatty acids progressively increase with the core depth. These results clearly show a utility of the compound-specific radiocarbon dating for developing sediment chronologies in the Antarctic margin sediments. This approach is potentially applicable to Arctic Ocean, as well as other areas of Southern Ocean where similar interferences by fossil or pre-aged carbon inputs have hindered the progress in the development of late Quaternary paleoceanographic records.