Scale distortion from pressure baselines as a source of inaccuracy in triple-isotope measurements.

RATIONALE: Isotope ratio measurements have become extremely precise in recent years, with many approaching parts-per-million (ppm) levels of precision. However, seemingly innocuous errors in signal baselines, which exist only when gas enters the instrument, might lead to significant errors. These "pressure-baseline" (PBL) offsets may have a variety of origins, such as incoherent scattering of the analyte, isobaric interferences, or electron ablation from the walls of the flight tube. They are probably present in all but ultra-high-resolution instruments, but their importance for high-precision measurements has not been investigated. METHODS: We derive the governing equations for the PBL effect. We compare the oxygen triple-isotope composition of gases on three different mass spectrometers before and after applying a correction for PBLs to determine their effects. We also compare the composition of atmospheric O2 with that of several standard minerals (San-Carlos Olivine and UWG-2) on two high-precision mass spectrometers and compare those results with the differences reported in the literature. RESULTS: We find that PBLs lead to stretching or compression of isotopic variations. The scale distortion is non-mass-dependent, affecting the accuracy of triple-isotope covariations. The governing equations suggest that linear stretching corrections using traditional isotopic delta values (e.g., δ18 O) are rigorous for PBL-induced errors in pure gases. When the reference and sample gases are not comparable in composition or purity, however, a different correction scheme may be required. These non-mass-dependent errors are systematic and may have influenced previous measurements of triple-isotope covariations in natural materials. CONCLUSIONS: Accurate measurements of isotopic variations are essential to biogeochemistry and for testing theoretical models of isotope effects. PBLs are probably ubiquitous, contributing to the interlaboratory disagreements in triple-isotope compositions of materials differing greatly in δ18 O values. Moreover, they may lead to inaccurate determination of triple-isotope compositions and fractionation factors, which has implications for isotopic studies in hydrology and biogeochemistry.

Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today1. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆17O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆17O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period2. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO2 and O2 and the photosynthetic O2 flux at this time3. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO2 (2-30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O2 was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean4-6 and Phanerozoic primary production7, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O2 over geologic time8.

Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event.

The ~635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently (17)O-depleted sulfate (SO4(2-)) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly (17)O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous (17)O signal was imparted to sulfate of oxidative weathering origin. However, (17)O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate (17)O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The (17)O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ(13)C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0-0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown.