The clumped isotopic composition of carbonate‐derived CO2 (denoted Δ47) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters: R13VPDB, R17VSMOW, R18VSMOW, and λ) impact calculated Δ47 values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ47 relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set (n = 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ47 relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ47 (Δ*25‐X), based on combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ47 relationship, but many more remain to be investigated.
PBL-corrected heated gas and equilibrated gas calibrations in bellows and micro-volume modes are nearly identical and stable through time. Introduction of the PBL correction, a revision to the absolute reference frame approach to determining Δ(47) values, dramatically improves the external precision of Δ(47) measurements to near instrumental analytical uncertainty (6-8 ppm (1σ) in bellows mode; 10-12 ppm in micro-volume mode).
The stable isotope compositions of carbonate and organic samples from the Oiyug basin in southern Tibet allows for model calculations of the Oligocene to Pliocene paleoelevation of the south central Tibetan Plateau. We measured the oxygen isotope composition of pedogenic and lacustrine calcite, dolomite, and siderite, and the hydrogen isotope composition of n-alkanes from plant waxes to reconstruct the ␦ 18 O and ␦D values of Oiyug basin paleometeoric water. Calculated water isotope values from Oiyug basin carbonate and organic samples, respectively, are in close agreement, suggesting the preservation of an unaltered paleometeoric water isotopic signal in these archives. Late Oligocene-middle Miocene paleoelevation estimates from groundwater/ pedogenic calcite and lacustrine dolomite indicate basin elevations of 4.1 km ؉1.2/ ؊1.6 km. Plant-wax n-alkanes ␦D and lacustrine-siderite ␦ 18 O compositions of middle Miocene (ϳ15 Ma) samples indicate paleoelevations of 5.1 km ؉1.3/؊1.9 km. This estimated elevation is similar to the 5.4 km paleoelevation estimate based on fossilfloral physiognomy from the same stratigraphic interval. Calculated late MiocenePliocene paleoelevation estimates derived from the ␦ 18 O composition of lacustrine marls and carbonate/siderite concretions, as well as the ␦D from plant wax n-alkanes indicate a mean elevation of 5.5 km ؉1.4/؊2.0 km at ϳ5 Ma. Although calculated mean paleoelevations for the Oiyug basin all fall within the errors associated with the model calculations, the close agreement of the different paleoelevation proxies provides an additional degree of confidence in the fidelity of the calculated paleoelevations. Calculated paleoelevations indicate a possible increase in Oiyug basin elevations of ϳ1.4 km between the early and late Miocene. Given the modern Oiyug basin elevation of ϳ4.3 km, study results allow for a possible >1 km decrease in elevation since the early Pliocene. These findings, in conjunction with other Tibetan paleoaltimetry studies, are consistent with tectonic models supporting high elevations of the Tibetan Plateau since the initiation of India-Asia collision during the Eocene, and subsequent late Cenozoic extensional collapse.
Methylene is one of, if not the, most reactive organic chemical known. It has a very low specificity, which makes it essentially useless for synthesis, but suggests a possible role in protein footprinting with special importance in labeling solvent accessible nonpolar areas, identifying ligand binding sites, and outlining interaction areas on protomers that form homo or hetero oligomers in cellular assemblies. The singlet species is easily and conveniently formed by photolysis of diazirine. The reactions of interest are insertion into C-H bonds and addition to multiple bonds, both forming strong covalent bonds and stable compounds. Reaction with proteins and peptides is reported even in aqueous solutions where the vast majority of the reagent is used up in forming methanol. Species containing up to 5 to 10 extra :CH 2 groups are easily detected by electrospray mass spectroscopy. In a mixture of a 14 K d protein and a noninteracting 1.7 K d peptide, the distribution of mass peaks in the electrospray spectra was close to that expected from random modification of the estimated solvent accessible area for the two molecules. For analysis at the single residue level, quantitation at labeling levels of one 13 CH 2 group per 10 to 20 kDa of protein appears to be possible with isotope ratio mass spectroscopy. In the absence of reactive solvents, photolysis of diazirine produces oily polymeric species that contain one or two nitrogen atoms, but not more, and are water soluble.
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