Search results for "SULFUR"

2017

Abstract. We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of su…

2012

Abstract. Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous m…

2012

Abstract. The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a …

2014

Abstract. Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enh…

A study on the fragmentation of sulfuric acid and dimethylamine clusters inside an atmospheric pressure interface time-of-flight mass spectrometer

2022

Abstract. Sulfuric acid and dimethylamine vapours in the atmosphere can form molecular clusters, which participate in new particle formation events. In this work, we have produced, measured, and identified clusters of sulfuric acid and dimethylamine using an electrospray ionizer coupled with a planar-differential mobility analyser, connected to an atmospheric pressure interface time-of-flight mass spectrometer (ESI–DMA–APi-TOF MS). This set-up is suitable for evaluating the extent of fragmentation of the charged clusters inside the instrument. We evaluated the fragmentation of 11 negatively charged clusters both experimentally and using a statistical model based on quantum chemical data. Th…

2012

Abstract. The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl…

2018

Abstract. Volcanoes are a natural source of several reactive gases (e.g., sulfur and halogen containing species) and nonreactive gases (e.g., carbon dioxide) to the atmosphere. The relative abundance of carbon and sulfur in volcanic gas as well as the total sulfur dioxide emission rate from a volcanic vent are established parameters in current volcano-monitoring strategies, and they oftentimes allow insights into subsurface processes. However, chemical reactions involving halogens are thought to have local to regional impact on the atmospheric chemistry around passively degassing volcanoes. In this study we demonstrate the successful deployment of a multirotor UAV (quadcopter) system with c…

The tropospheric processing of acidic gases and hydrogen sulphide in volcanic gas plumes as inferred from field and model investigations

2007

Abstract. Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chlori…

A predictive model for salt nanoparticle formation using heterodimer stability calculations

2021

Acid–base clusters and stable salt formation are critical drivers of new particle formation events in the atmosphere. In this study, we explore salt heterodimer (a cluster of one acid and one base) stability as a function of gas-phase acidity, aqueous-phase acidity, heterodimer proton transference, vapor pressure, dipole moment and polarizability for salts comprised of sulfuric acid, methanesulfonic acid and nitric acid with nine bases. The best predictor of heterodimer stability was found to be gas-phase acidity. We then analyzed the relationship between heterodimer stability and J4×4, the theoretically predicted formation rate of a four-acid, four-base cluster, for sulfuric acid salts ove…

Oscillatory Changes of the Heterogeneous Reactive Layer Detected with the Motional Resistance during the Galvanostatic Deposition of Copper in Sulfur…

2015

Metallic copper was galvanostatically deposited on quartz|gold resonant electrodes by applying a constant current in a 0.5 M CuSO4/0.1 M H2SO4 aqueous solution. Galvanostatic copper deposition is one of the best methodologies to calibrate the electrochemical quartz crystal microbalances (EQCM), a gravimetric sensor to evaluate changes in mass during the electrochemical reactions through the Sauerbrey equation. The simultaneous measurement of mass, current density, and motional resistance by an EQCM with motional resistance monitoring allows us to characterize the processes occurring on the electrode surface and at the interfacial regions with unprecedented detail. During the galvanostatic c…