Variability of sulfate signal in ice core records based on five replicate cores

International audienceCurrent volcanic reconstructions based on ice core analysis have significantly improved over the past few decades by incorporating multiple-core analyses with a high temporal resolution from different parts of the polar regions into a composite common volcanic eruption record. Regional patterns of volcanic deposition are based on composite records, built from cores taken at both poles. However, in many cases only a single record at a given site is used for these reconstructions. This assumes that transport and regional meteorological patterns are the only source of the dispersion of the volcanic products. Here we evaluate the local-scale variability of a sulfate profile in a low-accumulation site (Dome C, Antarctica), in order to assess the representativeness of one core for such a reconstruction. We evaluate the variability with depth, statistical occurrence, and sulfate flux deposition variability of volcanic eruptions detected in five ice cores, drilled 1 m apart from each other. Local-scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events when a single core is used as the site reference , with a bulk probability of 30 % of missing volcanic events and close to 65 % uncertainty on one volcanic flux measurement (based on the standard deviation obtained from a five-core comparison). Averaging n records reduces the uncertainty of the deposited flux mean significantly (by a factor 1/ √ n); in the case of five cores, the uncertainty of the mean flux can therefore be reduced to 29 %

Stratospheric aerosol - Observations, processes, and impact on climate

Interest in stratospheric aerosol and its role in climate have increased over the last decade due to the observed increase in stratospheric aerosol since 2000 and the potential for changes in the sulfur cycle induced by climate change. This review provides an overview about the advances in stratospheric aerosol research since the last comprehensive assessment of stratospheric aerosol was published in 2006. A crucial development since 2006 is the substantial improvement in the agreement between in situ and space-based inferences of stratospheric aerosol properties during volcanically quiescent periods. Furthermore, new measurement systems and techniques, both in situ and space based, have been developed for measuring physical aerosol properties with greater accuracy and for characterizing aerosol composition. However, these changes induce challenges to constructing a long-term stratospheric aerosol climatology. Currently, changes in stratospheric aerosol levels less than 20% cannot be confidently quantified. The volcanic signals tend to mask any nonvolcanically driven change, making them difficult to understand. While the role of carbonyl sulfide as a substantial and relatively constant source of stratospheric sulfur has been confirmed by new observations and model simulations, large uncertainties remain with respect to the contribution from anthropogenic sulfur dioxide emissions. New evidence has been provided that stratospheric aerosol can also contain small amounts of nonsulfate matter such as black carbon and organics. Chemistry-climate models have substantially increased in quantity and sophistication. In many models the implementation of stratospheric aerosol processes is coupled to radiation and/or stratospheric chemistry modules to account for relevant feedback processes

Variability of sulfate signal in ice core records based on five replicate cores

Current volcanic reconstructions based on ice core analysis have significantly improved over the past few decades by incorporating multiple-core analyses with a high temporal resolution from different parts of the polar regions into a composite common volcanic eruption record. Regional patterns of volcanic deposition are based on composite records, built from cores taken at both poles. However, in many cases only a single record at a given site is used for these reconstructions. This assumes that transport and regional meteorological patterns are the only source of the dispersion of the volcanic products. Here we evaluate the local-scale variability of a sulfate profile in a low-accumulation site (Dome C, Antarctica), in order to assess the representativeness of one core for such a reconstruction. We evaluate the variability with depth, statistical occurrence, and sulfate flux deposition variability of volcanic eruptions detected in five ice cores, drilled 1 m apart from each other. Local-scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events when a single core is used as the site reference, with a bulk probability of 30 % of missing volcanic events and close to 65 % uncertainty on one volcanic flux measurement (based on the standard deviation obtained from a five-core comparison). Averaging <i>n</i> records reduces the uncertainty of the deposited flux mean significantly (by a factor 1∕ <mo form="infix">√</mo> <i>n</i>); in the case of five cores, the uncertainty of the mean flux can therefore be reduced to 29 %

Cold decade (AD 1810–1819) caused by Tambora (1815) and another (1809) stratospheric volcanic eruption

International audienceClimate records indicate that the decade of AD 1810–1819 including “the year without a summer” (1816) is probably the coldest during the past 500 years or longer, and the cause of the climatic extreme has been attributed primarily to the 1815 cataclysmic Tambora eruption in Indonesia. But the cold temperatures in the early part of the decade and the timing of the Tambora eruption call into question the real climatic impact of volcanic eruptions. Here we present new evidence, based on sulfur isotope anomaly (Δ33S), a unique indicator of volcanic sulfuric acid produced in the stratosphere and preserved in polar snow, and on the precise timing of the volcanic deposition in both polar regions, that another large eruption in 1809 of a volcano is also stratospheric and occurred in the tropics. The Tambora eruption and the undocumented 1809 eruption are together responsible for the unusually cold decade

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis

International audienceRationalePrecise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution.MethodsOne mL of reducing solution made of HI and NaH2PO2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H2S was purged with inert gas (He or N2) through gas‐washing tubes and then collected by NaOH solution. The collected H2S was converted into Ag2S by adding AgNO3 solution and the co‐precipitated Ag2O was removed by adding a few drops of concentrated HNO3.ResultsWithin 2–3 h, a 100% yield was observed for samples with 0.2–2.5 μmol Na2SO4. The reduction rate was much slower for BaSO4 and a complete reduction was not observed. International sulfur reference materials, NBS‐127, SO‐5 and SO‐6, were processed with this method, and the measured against accepted δ34S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R2 value of 0.998.ConclusionsThe new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H2S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available

SO 2 Oxidation Kinetics Leave a Consistent Isotopic Imprint on Volcanic Ice Core Sulfate

International audienceThis work presents measurements of time-resolved mass-independently fractionated sulfate of volcanic origin from Antarctic ice core records that cover the last 2,600 years. These measurements are used to evaluate the time dependence of the deposited isotopic signal and to extract the isotopic characteristics of the reactions yielding sulfate from stratospheric volcanic eruptions in the modern atmosphere. Time evolution of the signal in snow (years) with respect to the fast SO 2 oxidation in the stratosphere suggests that photochemically produced condensed phase is rapidly and continuously separated from the gas phase and preserved during transportation and deposition on the polar ice cap. On some eruptions, a nonzero isotopic mass balance highlights that a part of the signal can be lost during transport and/or deposition. The large number of volcanic events studied allows the Δ 33 S versus Δ 36 S and δ 34 S versus Δ 33 S slopes to be constrained at À1.56 (1σ = 0.25) and 0.09 (1σ = 0.02), respectively. The Δ 33 S versus Δ 36 S slope refines a prior determinations of Δ 36 S/Δ 33 S = À4 and overlaps the range observed for sulfur seen in early Earth samples (Archean). In recent volcanogenic sulfate, the Δ 33 S versus δ 34 S differs, however, from the Archean record. The similitude for Δ 36 S/Δ 33 S and the difference for Δ 33 S/δ 34 S suggest similar mass-independently fractionated sulfate processes to the Archean atmosphere. Using a simple model, we highlight that a combination of several mechanisms is needed to reproduce the observed isotopic trends and suggest a greater contribution from mass-dependent oxidation by OH in the modern atmosphere. Plain Language Summary Large volcanic eruptions inject sulfurous gases in the stratosphere, where they rapidly form sulfuric acid aerosols. These aerosols can reside in the stratosphere for years, cover the entire globe, and profoundly modify the climate by scattering and absorbing solar radiation. Sulfuric acid aerosols formed by this process acquire an isotopic anomaly that traces these processes and allows identification of these eruptions in ice core records, providing a means to distinguish between high and low climatic impact eruptions in ice core volcanic deposits. This study provides a characterization of this time-dependent isotopic signature that is used to constrain its origin and to understand the processes underlying its production and evolution