Sulfur Anomaly Research Articles

On the Budget and Atmospheric Fate of Sulfur Emissions From Large Volcanic Eruptions

AbstractToday, volcanic sulfur emissions into the atmosphere are measured spectroscopically from the ground, air and space. For eruptions prior to the satellite era, two main sulfur proxies are used, the rock and ice core records, as illustrated by Peccia et al. (2023, https://doi.org/10.1029/2023gl103334). The first approach is based on calculations of the sulfur content of the magma, while the second uses traces of sulfur deposited in ice. Both approaches have their limitations. For glaciochemistry, the volcano responsible for a sulfur anomaly is often unknown and the atmospheric pathway by which the sulfur reached the ice uncertain. The petrologic method relies, too, on uncertain estimates of eruption size and a number of geochemical assumptions that are hard to verify. A deeper knowledge of processes occurring both within magma bodies prior to eruption, and within volcanic plumes in the atmosphere is needed to further our understanding of the impacts of volcanism on climate.

Whither or Wither the Sulfur Anomaly in Planetary Nebulae?

We present a thorough investigation of the long-standing sulfur anomaly enigma. Our analysis uses chemical abundances from the most extensive data set available for 126 planetary nebulae (PNs) with improved accuracy and reduced uncertainties from a 10° × 10° Galactic bulge region. By using argon as a superior PN metallicity indicator, the anomaly is significantly reduced and better constrained. For the first time in PNs we show sulfur α-element lockstep with both oxygen and argon. We dispel hypotheses that the anomaly originates from underestimation of higher sulfur ionization stages. Using a machine-learning approach, we show that earlier ionization correction factor schemes contributed significantly to the anomaly. We find a correlation between the sulfur anomaly and the age/mass of PN progenitors, with the anomaly either absent or significantly reduced in PNs with young progenitors. Despite inherent challenges and uncertainties, we link this to PN dust chemistry, noting those with carbon-dust chemistry show a more pronounced anomaly. By integrating these findings, we provide a plausible explanation for the residual, reduced sulfur anomaly and propose its potential as an indicator of relative galaxy age compositions based on PNs.

2017 Leonard Medal for Mark Thiemens

2017 Leonard Medal for Mark Thiemens

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

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 (Δ(33)S = +1.66‰ and Δ(36)S = +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 (Δ(36)S = -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.

THE CURIOUS CONUNDRUM REGARDING SULFUR ABUNDANCES IN PLANETARY NEBULAE

Sulfur abundances derived from optical emission line measurements and ionization correction factors in planetary nebulae are systematically lower than expected for the objects' metallicities. We have carefully considered a large range of explanations for this "sulfur anomaly", including: (1) correlations between the size of the sulfur deficit and numerous nebular and central star properties; (2) ionization correction factors which under-correct for unobserved ions; (3) effects of dielectronic recombination on the sulfur ionization balance; (4) sequestering of S into dust and/or molecules; and (5) excessive destruction of S or production of O by AGB stars. It appears that all but the second scenario can be ruled out. However, we find evidence that the sulfur deficit is generally reduced but not eliminated when S^+3 abundances determined directly from IR measurements are used in place of the customary sulfur ionization correction factor. We tentatively conclude that the sulfur anomaly is caused by the inability of commonly used ICFs to properly correct for populations of ionization stages higher than S^+2.

A detailed look at chemical abundances in the Magellanic Clouds

AbstractWe determine elemental abundances of He, N, O, Ne, S, and Ar in Magellanic Cloud planetary nebulae (PNe) using direct methods and a large set of observed ions, minimizing the need for ionization correction factors. In contrast to prior studies, we find a clear separation between Type I and non-Type I PNe in these low-metallicity environments, and no evidence that the O-N nucleosynthesis cycle is active in low-mass progenitors. We find that the S/O abundance ratio is anomalously low compared to H ii regions, confirming the “sulfur anomaly” found for Galactic PNe. We also found that Ne/O is elevated in some cases, raising the possibility that Ne yields in low-mass AGB stars may be enhanced at low metallicity.

Association between catastrophic paleovegetation changes during Devonian–Carboniferous boundary and the formation of giant massive sulfide deposits

The Iberian Pyrite Belt (SW Iberia) is one of the largest sulfur anomalies in the Earth's crust. In the southern Iberian Pyrite Belt, more than 820 Mt of exhalative massive sulfides were deposited in less than one million years at the Devonian–Carboniferous boundary. The shale of the ore-bearing horizon contains biomarkers indicating major biogenic activity in a methanogenic setting, including a five-fold increase in typical vascular plant biomarkers and a significant anomaly in those probably indicating the presence of thermophilic Archaea. This contrasts with signatures in the average sedimentary rocks of the basin that indicate the sediments settled in oxic to sub-oxic environments, and that they have only minor biomarkers derived from continental paleoflora. These data show that the formation of the mineralization was not only related to major hydrothermal activity synchronous with volcanism but may also have been controlled by the input of large amounts of organic matter, mostly derived from the degradation of woodland detritus sourced in the nearby continent. This massive influx of organic matter could have accelerated extremophilic microbial activity that used short-chain hydrocarbons as electron donors for seawater sulfate reduction, resulting in concomitant massive sulfide precipitation. We propose that the giant massive sulfide deposits resulted from overlapping of geological and biological processes that occurred at the Devonian to Carboniferous transition, including: (1) continent collision during the onset of the Variscan orogeny leading to major paleogeographic changes and volcanism; (2) dramatic stress of continental ecosystems due to the combination of climatic change, volcanism, variations in the sea level and erosion on a regional scale; (3) major biomass destruction and increase of organic supply to marine environments; and, (4) generation of anoxic conditions and the thriving of sulfate reducing microorganisms. Under these conditions, massive sulfide deposits formed where venting sulfur-poor but metal-rich hydrothermal brines flowed into a hydrogen sulfide-rich anoxic water column. The data presented strongly suggest that there was a temporal and causal relationship between the Devonian–Carboniferous geotectonic, climatic and biological crises and the formation of the giant volcano-sedimentary massive sulfide deposits of the southern Iberian Pyrite Belt.

The Sulfur Abundance Anomaly in Planetary Nebulae

The failure of S and O abundances in most planetary nebulae to display the same strong direct correlation that is observed in extragalactic H II regions represents one of the most perplexing problems in the area of PN abundances today. Galactic chemical evolution models as well as large amounts of observational evidence from H II region studies support the contention that cosmic abundances of alpha elements such as O, Ne, S, Cl, and Ar increase together in lockstep. Yet abundance results from the Henry, Kwitter, & Balick (2004) database show a strong tendency for most PNe to have S abundances that are significantly less than expected from the observed level of O. One reasonable hypothesis for the sulfur anomaly is the past failure to properly measure the abundances of unseen ionization stages above S^+2. Future observations with Spitzer will allow us to test this hypothesis.

Sulfur, Chlorine, and Argon Abundances in Planetary Nebulae. IV. Synthesis and the Sulfur Anomaly

We have compiled a large sample of O, Ne, S, Cl, and Ar abundances that have been determined for 85 Galactic planetary nebulae in a consistent and homogeneous manner using spectra extending from 3600 to 9600 A. Sulfur abundances have been computed using the near-IR lines of [S III] λλ9069, 9532 along with [S III] temperatures. We find average values, expressed logarithmically with a standard deviation, of log(S/O) = -1.91 ± 0.24, log(Cl/O) = -3.52 ± 0.16, and log(Ar/O) = -2.29 ± 0.18, numbers consistent with previous studies of both planetary nebulae and H II regions. We also find a strong correlation between [O III] and [S III] temperatures among planetary nebulae. In analyzing abundances of Ne, S, Cl, and Ar with respect to O, we find a tight correlation for Ne-O, and loose correlations for Cl-O and Ar-O. All three trends appear to be colinear with observed correlations for H II regions. S and O also show a correlation, but there is a definite offset from the behavior exhibited by H II regions and stars. We suggest that this S anomaly is most easily explained by the existence of S+3, whose abundance must be inferred indirectly when only optical spectra are available, in amounts in excess of what is predicted by model-derived ionization correction factors in PNe. Finally for the disk PNe, abundances of O, Ne, S, Cl, and Ar all show gradients when plotted against Galactocentric distance. The slopes are statistically indistinguishable from one another, a result which is consistent with the notion that the cosmic abundances of these elements evolve in lockstep.