Headspace solid phase microextraction – GC/C-IRMS for δ13CVPDB measurements of mono-aromatic hydrocarbons using EA-IRMS calibration
This work aims at comparing the δ13CVPDB of mono-aromatic hydrocarbons benzene, toluene, ethylbenzene and xylene isomers (BTEX) measured by elemental analyser (EA)-isotope ratio mass spectrometer (IRMS) with the δ13CVPDB measured on the same compounds by headspace solid phase microextraction – GC/C-IRMS (hSPME – GC/C-IRMS) with the final goal of using these compounds as internal standards on the latter system. The EA-IRMS measurements were done using calcium and lithium carbonate isotopic reference materials: NBS19 and L-SVEC for establishing the δ13CVPDB scale. The EA-IRMS measurements with helium dilution of a set of five reference materials (USGS40, USGS41, IAEA-CH-6, IAEA-CH-3 and IAEA-601) show systematic bias of 1‰ relative to their assigned values. This bias due to the dilution mechanism in the used ConfloII interface device could not be avoided. As the selected hydrocarbons: BTEX could not be analysed by EA-IRMS without helium dilution, their δ13CVPDB must be corrected from this observed bias using an external calibration. The CO2 gas calibrated using EA-IRMS without helium dilution, was used as an in-house reference for the δ13CVPDB measurements of the BTEX by the hSPME – GC/C-IRMS system. The comparison made between the δ13CVPDB measured on the same BTEX compounds by EA-IRMS (with external calibration) and by hSPME – GC/C-IRMS techniques showed good agreement.
ConFlo III – an interface for high precision δ13C and δ15N analysis with an extended dynamic range
A newly developed interface coupling a CHN combustion device (elemental analyser 'EA') to an isotope ratio mass spectrometer is described and evaluated. The purpose of the device is to extend the dynamic range of delta(13)C and delta(15)N analysis from less than 2 orders of magnitude to more than 3 orders of magnitude. Carbon isotope ratio measurements of atropine as a model compound have been performed analysing between 1 µg to 5 mg C with acceptable to excellent precision (0.6 to 0.06 per thousand, delta-notation). The correction due to the blank signal is critical for sample amounts smaller than 4 µg C. The maximum sample weight is determined by the combustion capacity of the EA. Larger sample amounts are measured using dilution of a small part of the EA effluent with helium. The dilution mechanism works virtually free of isotope fractionation. Copyright 1999 John Wiley & Sons, Ltd.
O2 constraints from Paleoproterozoic detrital pyrite and uraninite
Redox-sensitive detrital grains such as pyrite and uraninite in sedimentary successions provide one of the most conspicuous geological clues to a different composition of the Archean and early Paleoproterozoic atmosphere. Today, these minerals are rapidly chemically weathered within short transport distances. Prior to the rise of oxygen, low O2 concentrations allowed their survival in siliciclastic deposits with grain erosion tied only to physical transport processes. After the rise of oxygen, redox-sensitive detrital grains effectively vanish from the sedimentary record. To get a better understanding of the timing of this transition, we examined sandstones recorded in a scientifi c drill core from the South African 2.415 Ga Koegas Subgroup, a mixed siliciclastic and iron formation–bearing unit deposited on the western deltaic margin of the Kaapvaal craton in early Paleoproterozoic time. We observed detrital pyrite and uraninite grains throughout all investigated sandstone beds in the section, indicating the rise of oxygen is younger than 2.415 Ga. To better understand how observations of detrital pyrite and uraninite in sedimentary rocks can quantitatively constrain Earth surface redox conditions, we constructed a model of grain erosion from chemical weathering and physical abrasion to place an upper limit on ancient environmental O2 concentrations. Even conservative model calculations for deltaic depositional systems with suffi cient transport distances (approximately hundreds of kilometers) show that redox-sensitive detrital grains are remarkably sensitive to environmental O2 concentrations, and they constrain the Archean and early Paleoproterozoic atmosphere to have <3.2 × 10 –5 atm of molecular O2. These levels are lower than previously hypothesized for redox-sensitive detrital grains, but they are consistent with estimates made from other redox proxy data, including the anomalous fractionation of sulfur isotopes. The binary loss of detrital pyrite and uraninite from the sedimentary record coincident with the rise of oxygen indicates that atmospheric O2 concentrations rose substantially at this time and were never again suffi ciently low (<0.01 atm) to enable survival and preservation of these grains in short transport systems.