Sulphur speciation of PM10 samples by XANES spectroscopy

Abstract

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to identify sulphur compounds in PM10 samples collected simultaneously at two sites with different environmental situations in the province of Trieste (NE of Italy), during summer and winter seasons respectively. The first site is an industrial site located near a steel mill plant and the second is a coastal site. The sulphur speciation at the industrial site has shown the presence of the following sulphur compounds in both seasons: organic compounds (thiophenes or Polycyclic Aromatic Sulphur Heterocycles -PAHs) and sulphates while in the winter season sulphites were also present. In the coastal site organic compounds (thiophenes or PASHs) and sulphate were found during winter season, moreover bisulphates were found during summer season. Relative percentages of the different sulphur compounds have shown that sulphate is the most abundant form of sulphur in the industrial site samples during both seasons and in the coastal site sample collected during the winter season (> 98%); in the coastal site sample collected during the summer season the relative percentages of bisulphate and sulphate were around 40% and 60% respectively.. © Versita Warsaw and Springer-Verlag Berlin Heidelberg.

Electrochemical Evidence of non-Volatile Reduced Sulfur Species in Water-Soluble Fraction of Fine Marine Aerosols

“…Results from this work are supportive to studies reporting a significant concentration of non-sulfate sulfur species in fine aerosols [33][34][35]47]. Besides organosulfates, additional sulfur species such as methanesulfonates, hydroxymethanesulfonates, sulfites, sulfides, polycyclic aromatic sulfur heterocycles, and primary biological particles were reported to contribute to non-sulfate sulfur species.…”

“…Sulfur in aerosols is usually measured in the form of inorganic sulfate ion, and it is often assumed to be one of the most important forms of aerosol S. However, in addition to sulfate, other S compounds, even in smaller quantities, are present in ambient aerosols. Among these, the most abundant are sulfides, organosulfur/sulfate compounds, and polycyclic aromatic sulfur heterocycles (PAHSs) [33][34][35]. Even though different methodological approaches have been applied to resolve S content in aerosols, including ion chromatography, X-ray fluorescence, and inductively coupled plasma mass spectrometry, these cannot determine the oxidation state or directly identify the chemical form of aerosol S. Thus, there is still a need for accurate and direct method enabling speciation of different S species in small amounts such as those found within PM 2.5 and/or PM 10 samples (usually no more than a few milligrams).…”

Photodegradation of methyl thioglycolate particles as a proxy for organosulphur containing droplets

“…Although the (photo)reactivity of sulphur compounds in the atmosphere is complex and has been widely explored in the gaseous phase, 12,13 (photo)transformation of particles containing dissolved organosulphur compounds has been neglected. 14,15 Recently, Gaston et al 11 measured primary marine particles containing reduced sulphur, detected as elemental sulphur ions, in seven field campaigns conducted in various marine environment. Strong diurnal profile of these particles was explained by the marine biogenic activity and the rapid destruction of the sulphur-containing compounds during the daytime due to photolysis.…”

Composition and oxidation state of sulfur in atmospheric particulate matter

“…Primary emission sources of S +VI include both anthropogenic and biogenic sources, including combustion of fossil fuels, biomass burning, volcanoes, and sea spray (Querol et al, 2000). Sulfur in aerosol, ranging in oxidation state from S −II to S +IV , has also been identified in smaller quantities through the use of XANES techniques (Huggins et al, 2000;Eatough et al, 1978;Cao et al, 2015;Higashi and Takahashi, 2009;Craig et al, 1974;Cozzi et al, 2009). Primary sources of reduced sulfur to the atmosphere are mainly attributed to gaseous emissions from volcanic gases, hot springs, bacteria, vehicle exhaust, and oil refineries (Cozzi et al, 2009;Andersson et al, 2006).…”