New-on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

The origin of brines underlying Lake Kinneret

Lake Kinneret (LK) is a relatively fresh water take situated in the Dead Sea Rift (DSR) Valley. The pore water (PW) in the sediments underlying LK pelagic zone have significantly higher salinity than that of the lake. The concentrations of major ion solutes (Cl, Br, Na, K, Mg) in PW from six 2.4 m to 5.1 m long sediment cores increase linearly with depth, indicating the occurrence of saline, deep seated brines. The upper part of the PW column is affected by the much fresher boundary with LK water and in most cores is characterized by gradually increasing Br/Cl and decreasing Na, Mg, K/Cl molar ratios, which tend to stabilize at about 2.0 m below the sediment surface. The 'stable' molar ratios in the deeper PW vary spatially and are supposed to represent the ratios in the deep underlying brines at each site. When plotted as Na/Cl vs. Br/Cl, the stable ratios of the northern and central part of the lake fall close to a straight line which characterizes many of the brines in the DSR Valley. However, the respective ratios in the southern part of the lake fall markedly off the DSR line. Moreover, Na/Cl and K/Cl molar ratios in the south are significantly higher than in the central and northern parts. delta Cl-37 measured in present LK water is ca. 0.0 parts per thousand. Along the PW column at the lake center, delta Cl-37 is becoming more positive with depth, reaching values of about +0.5 parts per thousand to +0.6 parts per thousand at 3 m depth. Even more positive values (+0.7 parts per thousand to +0.8 parts per thousand) are detected further north, in PW from deeper sediment layers. In contrast, in PW from the southeastern part of the lake, delta Cl-37 is becoming more negative with depth (-1.0 parts per thousand at similar to 2.6 m). It is suggested that these isotopic differences are also indicative of spatial variability in the PW brine sources. O-18 and D values in the PW of all 3 m long cores are similar and resemble the respective levels in LK. The source of H2O in 3 m deep, bed sediments is claimed to be the overlying lake water, and therefore water isotopes do not provide a clue regarding the original water isotopic composition in the underlying brines. PW from the southeast with higher K/Cl and Na/Cl but lower concentrations of these solutes, suggest leaching by meteoric water of sub-surface halite and post-halite salt formations, while the more saline PW from the northern and central parts, that have lower K/Cl and Na/Cl, and higher Br/Cl, are similar to DSR brines and represent underlying residual brines. (C) 2009 Elsevier B.V. All rights reserved.

Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an in-situ optical nitrate sensor and dual nitrate isotopes

We investigated diurnal nitrate (NO3-) concentration variability in the San Joaquin River using an in situ optical NO3- sensor and discrete sampling during a 5-day summer period characterized by high algal productivity. Dual NO3- isotopes (delta N-15(NO3) and delta O-18(NO3)) and dissolved oxygen isotopes (delta O-18(DO)) were measured over 2 days to assess NO3- sources and biogeochemical controls over diurnal time-scales. Concerted temporal patterns of dissolved oxygen (DO) concentrations and delta O-18(DO) were consistent with photosynthesis, respiration and atmospheric O-2 exchange, providing evidence of diurnal biological processes independent of river discharge. Surface water NO3- concentrations varied by up to 22% over a single diurnal cycle and up to 31% over the 5-day study, but did not reveal concerted diurnal patterns at a frequency comparable to DO concentrations. The decoupling of delta N-15(NO3) and delta O-18(NO3) isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO3- variability in the San Joaquin River during the study. The lack of a clear explanation for NO3- variability likely reflects a combination of riverine biological processes and time-varying physical transport of NO3- from upstream agricultural drains to the mainstem San Joaquin River. The application of an in situ optical NO3- sensor along with discrete samples provides a view into the fine temporal structure of hydrochemical data and may allow for greater accuracy in pollution assessment.

Late Quaternary environmental change in the interior South American tropics: new insight from leaf wax stable isotopes

Stable isotope analysis of leaf waxes in a sediment core from Laguna La Gaiba, a shallow lake located at the Bolivian margin of the Pantanal wetlands, provides new perspective on vegetation and climate change in the lowland interior tropics of South America over the past 40,000 years. The carbon isotopic compositions (δ13C) of long-chain n-alkanes reveal large shifts between C3-and C4-dominated vegetation communities since the last glacial period, consistent with landscape reconstructions generated with pollen data from the same sediment core. Leaf wax δ13C values during the last glacial period reflect an open landscape composed of C4grasses and C3herbs from 41–20ka. A peak in C4abundance during the Last Glacial Maximum (LGM, ∼21ka) suggests drier or more seasonal conditions relative to the earlier glacial period, while the development of a C3-dominated forest community after 20 ka points to increased humidity during the last deglaciation. Within the Holocene, large changes in the abundance of C4 vegetation indicate a transition from drier or more seasonal conditions during the early/mid-Holocene to wetter conditions in the late Holocene coincident with increasing austral summer insolation. Strong negative correlations between leaf wax δ13C and δD values over the entire record indicate that the majority of variability in leaf wax δD at this site can be explained by variability in the magnitude of biosynthetic fractionation by different vegetation types rather than changes in meteoric water δD signatures. However, positive δD deviations from the observed δ13C–δD trends are consistent with more enriched source water and drier or more seasonal conditions during the early/mid-Holocene and LGM. Overall, our record adds to evidence of varying influence of glacial boundary conditions and orbital forcing on South American Summer Monsoon precipitation in different regions of the South American tropics. Moreover, the relationships between leaf wax stable isotopes and pollen data observed at this site underscore the complementary nature of pollen and leaf wax δ13C data for reconstructing past vegetation changes and the potentially large effects of such changes on leaf wax δD signatures.

“Pussy cat, pussy cat where have you been..?” Evaluating the use of stable isotopes, radiogenic isotopes and trace elements for investigating the ecology of Panthera leo

1. Understanding the behaviour and ecology of large carnivores is becoming increasingly important as the list of endangered species grows, with felids such as Panthera leo in some locations heading dangerously close to extinction in the wild. In order to have more reliable and effective tools to understand animal behaviour, movement and diet, we need to develop novel, integrated approaches and effective techniques to capture a detailed profile of animal foraging and movement patterns. 2. Ecological studies have shown considerable interest in using stable isotope methods, both to investigate the nature of animal feeding habits, and to map their geographical location. However, recent work has suggested that stable isotope analyses of felid fur and bone is very complex and does not correlate directly with the isotopic composition of precipitation (and hence geographical location). 3. We present new data that suggest these previous findings may be atypical, and demonstrate that isotope analyses of Felidae are suitable for both evaluating dietary inputs and establishing geo-location as they have strong environmental referents to both food and water. These data provide new evidence of an important methodology that can be applied to the family Felidae for future research in ecology, conservation, wildlife forensics and archaeological science.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a central European cave (NW Switzerland)

Deuterium (dD) and oxygen (d18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of d17O and d18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (dD, d17O and d18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean dD, d18O and d17O are �71.0‰, �9.9‰, �5.2‰ for precipitation, �60.3‰, �8.7‰, �4.6‰ for cave drip water and �61.3‰, �8.3‰, �4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (D of ~ þ 10‰ for dD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8e10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first d17O measurement in speleothem fluid inclusions, as well as the first comparison of the d17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.