Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Kaiser, Jan

doi:10.1016/j.gca.2007.12.011

Cited by 68 publications

(110 citation statements)

References 73 publications

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“…Specifically, the relative 17 O/ 16 O isotope ratio difference of stratospheric CO 2 to tropospheric CO 2 is about 1.7 times that of the 18 O/ 16 O isotope ratio difference (Lämmerzahl et al, 2002), significantly higher than the factor of 0.516 ± 0.015 expected for many mass-dependent fractionation processes (Kaiser, 2008). Since O 2 is the source of the oxygen atoms in the short-lived O 3 molecule, this leads to corresponding 17 O depletion in atmospheric O 2 .…”

Section: 2)mentioning

confidence: 71%

“…Since 17 r r ≈ 0.000387, 18 r r = 0.002053 (Kaiser, 2008), 17 δ P 1 and 18 δ P 1, P ≈ P total . The correction from P to P total is less than 0.25 % and therefore negligibly small compared with other uncertainties that enter into the calculation of P from triple isotope measurements.…”

Section: Budget Calculationsmentioning

confidence: 99%

“…Generally, κ and λ may be derived from empirical relationships, e.g. κ = 0.515 in the case of a study on N 2 O (Cliff and Thiemens, 1997) or λ = 0.5279 for meteoric waters (Barkan and Luz, 2007), or may be based on theoretical predictions (Young et al, 2002;Kaiser, 2008).…”

Section: Quantification Of Deviations From Mass-dependent Isotope Ratmentioning

confidence: 99%

“…More neutral terms such as " 17 O excess" (Kaiser et al 2003;Angert et al, 2004;Barkan and Luz, 2007) and " 17 O balance" (Kaiser, 2008) have been suggested. " 17 O excess" has been adopted most widely and I will use this term here for 17 values.…”

Section: Quantification Of Deviations From Mass-dependent Isotope Ratmentioning

confidence: 99%

“…18 ε I , 17 ε I , 18 ε E , 17 ε E The kinetic isotope fractionation during O 2 invasion was measured as 18 ε I = (−2.8 ± 0.2) ‰ (Knox et al, 1992). I am not aware of any triple oxygen isotope studies of the corresponding 17 O/ 16 O isotope fractionation and therefore adopt 17 ε I = (1 + 18 ε I ) θ -1, with θ = 0.516 ± 0.015, covering the theoretically predicted range for mass-dependent isotope effects (Kaiser, 2008).…”

Section: Photosynthesismentioning

confidence: 99%

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Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Kaiser

2011

Biogeosciences

144

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Abstract. Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17 O excess and often used an approximation to derive production rates from the 17 O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17 O/ 16 O and 18 O/ 16 O isotope ratio differences (delta values) directly. I call this the "dual delta method". The 17 O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production.In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state.I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17 O excess of dissolved O 2 in equilibrium with atmospheric O 2 and the 17 O excess of photosynthetic O 2 need to be re-measured. Because of these uncertainties, all calculaCorrespondence to: J. Kaiser (j.kaiser@uea.ac.uk) tion parameters should always be fully documented and the measured relative isotope ratio differences as well as the oxygen supersaturation should be permanently archived, so that improved measurements of the calculation parameters can be used to retrospectively improve production rates.

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Section: 2)mentioning

confidence: 71%

Section: Budget Calculationsmentioning

confidence: 99%

Section: Quantification Of Deviations From Mass-dependent Isotope Ratmentioning

confidence: 99%

Section: Quantification Of Deviations From Mass-dependent Isotope Ratmentioning

confidence: 99%

Section: Photosynthesismentioning

confidence: 99%

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Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Kaiser

2011

Biogeosciences

144

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Current literature in mass spectrometry

2008

J. Mass Spectrom.

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In order to keep subscribers up‐to‐date with the latest developments in their field, John Wiley & Sons are providing a current awareness service in each issue of the journal. The bibliography contains newly published material in the field of mass spectrometry. Each bibliography is divided into 11 sections: 1 Reviews; 2 Instrumental Techniques & Methods; 3 Gas Phase Ion Chemistry; 4 Biology/Biochemistry: Amino Acids, Peptides & Proteins; Carbohydrates; Lipids; Nucleic Acids; 5 Pharmacology/Toxicology; 6 Natural Products; 7 Analysis of Organic Compounds; 8 Analysis of Inorganics/Organometallics; 9 Surface Analysis; 10 Environmental Analysis; 11 Elemental Analysis. Within each section, articles are listed in alphabetical order with respect to author (4 Weeks journals ‐ Search completed at 25th. June 2008)

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Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O₂, CO, CO₂, N₂O and SO₂

Kaiser¹,

Röckmann²

2008

Rapid Comm Mass Spectrometry

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Gas isotope ratio mass spectrometers usually measure ion current ratios of molecules, not atoms. Often several isotopologues contribute to an ion current at a particular mass-to-charge ratio (m/z). Therefore, corrections have to be applied to derive the desired isotope ratios. These corrections are usually formulated in terms of isotope ratios (R), but this does not reflect the practice of measuring the ion current ratios of the sample relative to those of a reference material. Correspondingly, the relative ion current ratio differences (expressed as delta values) are first converted into isotopologue ratios, then into isotope ratios and finally back into elemental delta values. Here, we present a reformulation of this data reduction procedure entirely in terms of delta values and the 'absolute' isotope ratios of the reference material. This also shows that not the absolute isotope ratios of the reference material themselves, but only product and ratio combinations of them, are required for the data reduction. These combinations can be and, for carbon and oxygen have been, measured by conventional isotope ratio mass spectrometers. The frequently implied use of absolute isotope ratios measured by specially calibrated instruments is actually unnecessary. Following related work on CO2, we here derive data reduction equations for the species O2, CO, N2O and SO2. We also suggest experiments to measure the required absolute ratio combinations for N2O, SO2 and O2. As a prelude, we summarise historic and recent measurements of absolute isotope ratios in international isotope reference materials.

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Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Cited by 68 publications

References 73 publications

Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Current literature in mass spectrometry

Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O₂, CO, CO₂, N₂O and SO₂

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Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Cited by 68 publications

References 73 publications

Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

Current literature in mass spectrometry

Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O2, CO, CO2, N2O and SO2

Contact Info

Product

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Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O₂, CO, CO₂, N₂O and SO₂