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RATIONALE The condition of the pyrolysis reactor is very important for obtaining stable, precise hydrogen isotopic ratios using gas chromatography/thermal conversion/isotope ratio mass spectrometry (GC/TC/IRMS). However, few studies of the conditioning process have been conducted, and little is known about the best methods for high-precision hydrogen isotope analysis. METHODS We investigated δ2H variations and observed the changes in carbon coating using six different conditioning methods for the pyrolysis alumina tube: (i) no treatment; (ii) conditioning with 4 μL hexane; (iii) conditioning with 2 μL hexane; (iv) conditioning with 2 μL hexane followed by backflushing overnight; (v) conditioning with 10 s of backflushing with methane; (vi) conditioning with 3 s of backflushing with methane. RESULTS Conditioning the alumina tube can improve the pyrolysis efficiency of organic compounds because a moderate amount of carbon acts as a catalyst in high-temperature regions of the alumina tube. Carbon actually flows in the tube and is difficult to confine to the high-temperature region. Insufficient amounts of carbon in the high-temperature regions lead to incomplete pyrolysis of organic compounds and lower δ2H values due to kinetic fractionation of hydrogen isotopes. In contrast, excess hexane or methane can lead to higher δ2H values, probably due to enrichment of deuterium in the hydrocarbon residue. CONCLUSIONS The δ2H values obtained by Method 6 are closest to the TC/EA δ2H values and are more precise than those obtained by other methods, perhaps because this method introduces a moderate, consistent amount of carbon with each sample injection. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

We have investigated carbon isotopic compositions of four plant genus/species, Bothriochloa ischaemum (C4), Stipa bungeana (C3), Lespedeza sp. (C3) and Heteropappus less (C3), along a precipitation gradient in northwest China in order to assess the impact of water availability on the carbon isotopic discrimination against 13C during carbon assimilation in this area. This information is necessary for reconstruction of paleovegetation, particularly paleo-C3/C4 plant ratios using δ13C value of organic matter in loess and paleosols in the Chinese Loess Plateau. The δ13C of C3 plants, as a group, exhibits a negative correlation with the annual precipitation amount with a total change and sensitivity of 5‰ and −1.1‰/100 mm, respectively, for the precipitation range from 200 to 700 mm. The C4 grass, B. ischaemum responds to aridity by decreasing 1.7‰ for over the precipitation range from 350 to 700 mm; the plant δ13C is significantly correlated with annual precipitation with a slope −0.61‰/100 mm. This result implies that without considering the effect of water availability on the plant δ13C values, reconstruction of percent C4 vegetation during the last glaciation can be overestimated by about a factor of two. [ABSTRACT FROM AUTHOR]

The hydrogen isotopic composition of plant wax (δD wax ) inherits the isotopic values of the source water and isotopic fractionation that take place in lipid biosynthesis. The δD wax values of n -alkanes or n -acids in sediment records are considered to be effective paleo-δD for precipitation proxies for different timescales. However, the vegetation effect also contributes substantially to the apparent fractionation values (ε w-p ) between the precipitation and plant. Therefore, a method for evaluating the dominant plant source in the sediment records is key for reconstructing a reliable paleo-δD p record. In this study, based on field data from the extremely arid Qaidam Basin and the semi-arid central Chinese Loess Plateau (CLP), a plant type index (Pta), based on the traditional P aq and n -alkane C 31 /C 29 index, was used to evaluate the dominant plant type that contributed to the sediments. In the arid and semi-arid region, the Pta values of the aquatic plants were <90, while the shrub Pta ranged from 90 to 180 and the grass Pta was >180. A test on contemporary soils and surface lake sediments also showed that the Pta index could estimate the regional vegetation distribution in modern environments. We also evaluated the dominant n -alkane source for four sediment records in China during the last millennium and reconstructed a regional paleo-δD p by choosing a different ε w-p . The estimated paleo-δD p values showed a good correlation with the modern regional summer δD p . We suggest that a large number of field studies are needed to improve the Pta index for quantitatively calculating the precise ratios for various plant sources. Such data would play a key role in improving hydrogen isotopic hydroclimatic research. [ABSTRACT FROM AUTHOR]

The expansion of plants using the C4 photosynthetic pathway is one of the most prominent changes in the global ecosystem during the Cenozoic Era. A significant late Miocene expansion is well documented. However, the existence and cause of subsequent expansions are still not clear, owing in part to the lack of long, continuous climate-vegetation records. Here we present two high-resolution carbon isotope time series, covering the past 7 m.y., derived from eolian deposits on the Chinese Loess Plateau. The data indicate three intervals of significant C4 plant expansions within the semiarid monsoonal region of East Asia (ca. 2.9-2.7 Ma, 1.3-0.9 Ma, and 0.6 Ma-present). These expansions covary with strengthened East Asian summer monsoon circulation. We conclude that in East Asia, large-scale late Miocene C4/C3 vegetation changes in semiarid areas have been primarily driven by warm seasonal precipitation and temperature variations associated with changes in monsoon circulation. [ABSTRACT FROM AUTHOR]