Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate

Schauer, Andrew J.; Kunasek, S. A.; Sofen, E. D.; Erbland, Joseph; Savarino, Joël; Johnson, Benjamin W.; Amos, H. M.; Shaheen, R.; Abaunza, Mariana; Jackson, Terri; Thiemens, M. H.; Alexander, Becky

doi:10.1002/rcm.6332

Cited by 31 publications

(122 citation statements)

References 46 publications

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“…The O 2 gas obtained from pyrolysis of Ag 2 SO 4 in a quartz tube at a temperature of 1030°C was purified through a gas chromatograph and used for triple oxygen isotopes by an isotope ratio mass spectrometry (MAT253). The mass‐independent fractionation process of pyrolysis using quartz tube was corrected by the equation Δ 17 O = Δ 17 O quartz × 1.14 + 0.06 as determined by Schauer et al [].…”

Section: Methodsmentioning

confidence: 99%

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer

Lin

Zhang

et al. 2016

JGR Atmospheres

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The Himalayas were recently identified as a global hot spot for deep stratosphere-to-troposphere transport (STT) in spring. Although the STT in this region may play a vital role in tropospheric chemistry, the hydrological cycle and aquatic ecosystems in Asia, there is no direct measurement of a chemical stratospheric tracer to verify and evaluate its possible impacts. Here we use cosmogenic 35 S as a tracer for air masses originating in the stratosphere and transported downward. We measure concentrations of 35 S in fresh surface snow and river runoff samples collected from Mount Everest in April 2013 to be more than 10 times higher than previously reported by any surface measurement, in support of the Himalayas as a gateway of springtime STT. In light of this result, measurements of 35 SO 2 and 35 SO 4 2À at Nam Co in spring 2011 are reanalyzed to investigate the magnitudes of stratospheric air masses from the Himalayas to the tropospheric sulfur cycle and surface O 3 level over the Tibetan Plateau. A simple one-box model reveals that the oxidative lifetime of SO 2 is reduced in aged STT plumes. Triple oxygen isotopic measurements of sulfate samples suggest that enhanced O 3 levels may shift the oxidation pathway of SO 2 in the troposphere, which may be constrained by further intensive sampling and measurements. Comparison with surface O 3 measurements and traditional meteorological tracing methods shows that 35 S is a potentially unique and sensitive tracer to quantify the contribution of stratospheric air to surface O 3 levels in fresh or aged STT plumes.

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Section: Methodsmentioning

confidence: 99%

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer

Lin

Zhang

et al. 2016

JGR Atmospheres

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“…These samples were combined in a prior study to obtain sufficient sample for the oxygen-triple isotope measurements of nitrates, and the remaining solution was used for oxygen-triple isotope analysis of sulfates. Oxygen-triple isotopic composition was measured using a Thermo Finnigan Mat-253 Isotope Ratio mass spectrometer and corrected for high-temperature oxygen-isotope exchange with quartz (64). The reported sample dates are calculated from an average annual snow accumulation rate; therefore, actual dates in composite samples may be shifted by ±4 mo, which defines the maximal uncertainty in time.…”

Section: Methodsmentioning

confidence: 99%

Tales of volcanoes and El-Niño southern oscillations with the oxygen isotope anomaly of sulfate aerosol

Shaheen

Abauanza

Jackson

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO 4 ) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO 4 aerosol is linked to the ozone variation in the tropical upper troposphere/ lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher Δ 17 O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO 4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and Δ 17 O = 3.3‰, OEI = 11 and Δ 17 O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that Δ 17 O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations.

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“…Several approaches are currently available for the analytical determination of Δ 17 O(NO 3 – ) and/or Δ 17 O(SO 4 2– ) . The bacterial denitrifier method uses denitrifying bacteria to convert the nitrate ion into N 2 O gas .…”

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confidence: 99%

“…This method generates O 2 from pyrolysis of silver salts (AgNO 3 , Ag 2 SO 4 ) for isotopic analysis with sample size requirements >10 µmol for nitrate and > 1 µmol for sulfate . The pyrolysis method was further modified to be automated by coupling a Temperature Conversion/Elemental Analyzer (TC/EA) with a Finnigan MAT253 isotope ratio mass spectrometer in a continuous‐flow system (referred to as the TC/EA‐IRMS method hereafter). However, this automated TC/EA‐IRMS method also requires large sample sizes (>4 µmol for nitrate and >2 µmol for sulfate).…”

mentioning

confidence: 99%

Analysis of oxygen‐17 excess of nitrate and sulfate at sub‐micromole levels using the pyrolysis method

Geng

Schauer

Kunasek

et al. 2013

Rapid Comm Mass Spectrometry

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Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate

Cited by 31 publications

References 46 publications

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer

Tales of volcanoes and El-Niño southern oscillations with the oxygen isotope anomaly of sulfate aerosol

Analysis of oxygen‐17 excess of nitrate and sulfate at sub‐micromole levels using the pyrolysis method

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Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate

Cited by 31 publications

References 46 publications

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic 35S tracer

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic 35S tracer

Tales of volcanoes and El-Niño southern oscillations with the oxygen isotope anomaly of sulfate aerosol

Analysis of oxygen‐17 excess of nitrate and sulfate at sub‐micromole levels using the pyrolysis method

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Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer

Resolving the impact of stratosphere‐to‐troposphere transport on the sulfur cycle and surface ozone over the Tibetan Plateau using a cosmogenic ³⁵S tracer