Justin R. McCabe

Oxygen and sulfur isotopic composition of volcanic sulfate aerosol at the point of emission

Volcanic sulfate aerosol is emitted from the vents of many active volcanoes, but its origin has not yet been explained. We report the first measurements of the isotopic compositions of near-vent volcanic aerosol sulfate and use the combined sulfur and oxygen isotope systematics of the aerosol and magma at Masaya volcano, Nicaragua, to draw preliminary conclusions about the production mechanism of near-source volcanic sulfate. The sulfate aerosol does not display a significant mass-independent oxygen or sulfur isotopic signature, which suggests that primary volcanic aerosol does not contribute to the larger mass-independent anomalies found in some ambient atmospheric aerosols and as preserved in ice cores. The oxygen isotope composition of the sulfate appeared to become heavier on the particle filters with increasing amount of sample collected and suggests that the δ 18O value of the sulfate aerosol is <8‰. The sulfur isotopic composition of the sulfate did not vary with sample loading on the filters and had a mean δ 34S value of 7.7 ± 0.8‰, similar to that of the magma (6.6 ± 0.2‰). The low Δ17O value, the δ 18O value of the magma (6.6 ± 0.3‰) and the high δ 18O value of atmospheric oxygen (23.5‰) suggest that known atmospheric oxidation pathways at ambient temperatures are not the major routes of production for this sulfate. Instead, the isotopic systematics of aerosol and magma are consistent with sulfate production either by high-temperature equilibration of the magmatic gas mixture with small amounts of atmospheric oxygen or by direct emission of SO4 2− from the magma.

Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice

We recently reported the first multiple oxygen isotope composition of nitrate (NO_3^−) in ice cores (Alexander et al., 2004). Postdepositional photolysis and volatilization may alter the isotopic signatures of snowpack nitrate. Therefore the precise assessment of the geochemical/atmospheric significance of O-isotopic signatures requires information on the relative rates of photolysis (λ > 300 nm) of N^(16)O_3^−, N^(16)O_2^(17)O^−, and N^(16)O_2^(18)O^− in ice. Here we report on ^(17)O^- and ^(18)O^-fractionation in the 313-nm photolysis of 10-mM aqueous solutions of normal Fisher KNO3 (i.e., Δ17O = −0.2 ± 0.2‰) and 17O-enriched USGS-35 NaNO_3 (Δ^(17)O = 21.0 ± 0.4‰) between −30° and 25°C. We found that Fisher KNO_3 undergoes mass-dependent O-fractionation, i.e., a process that preserves Δ^(17)O = 0. In contrast, Δ^(17)O in USGS-35 NaNO_3 decreased by 1.6 ± 0.4‰ and 2.0 ± 0.4‰ at 25°C, 1.2 ± 0.4‰ and 1.3 ± 0.4‰ at −5°C, and 0.2 ± 0.4‰ and 1.1 ± 0.4‰ at −30°C, after 12 and 24 hours, respectively. Since the small quantum yield (∼0.2%) of NO_3^− photodecomposition into (NO_2 + OH) is due to extensive cage recombination of the primary photofragments rather than to intramolecular processes, the observed Δ^(17)O decreases likely reflect competitive O-isotope exchange of geminate OH-radicals with H_2O (Δ^(17)O = 0) and escape from the solvent cage, in addition to residual O-isotope mixing of the final photoproducts NO, NO_2, NO_2^−, with H_2O. At the prevailing low temperatures, photochemical processing will not impair the diagnostic value of O-isotopic signatures in tracing the chemical ancestry of nitrate in polar ice.

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

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 (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 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 ∆17O 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 SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and ∆17O = 3.3‰, OEI = 11 and ∆17O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that ∆17O 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.

Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere

Significance The highest S-isotope anomaly is observed in a nonvolcanic period, and the magnitude of anomaly is similar to the largest volcanic eruptions of the 20th century. S-quadruple isotope data provided the first evidence of how super El Niño Southern Oscillation (ENSO) events (1997–1998) have affected the transport and transformation of aerosols to the stratosphere; thus, record of paleo-ENSO events of this magnitude can be traced with the S-isotopic anomaly. High-resolution and high-precision S-isotopic fingerprinting also revealed that the tropospheric sulfate produced during fossil-fuel and biomass burning contributes to the stratospheric sulfate aerosol layer, a contribution previously unrecognized. The distribution of sulfur anomalies mimics the Archean isotope record, which is used to track the origin and evolution of oxygen on earth. Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984–2001) showed the highest S-isotopic anomalies (Δ33S = +1.66‰ and Δ36S = +2‰) in a nonvolcanic (1998–1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997–1998)-induced changes in troposphere–stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ36S = −0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.