Gaseous Sulfuric Acid Concentrations Research Articles

Characterization, Sources, and Chemical Processes of Submicron Aerosols at a Mountain Site in Central China

AbstractA field campaign (29 May to 14 June 2018) was conducted at a mountain site in central China. The chemical composition of non‐refractory submicron particulate matter (NR‐PM1) and the particle number size distribution (PNSD) were measured, respectively. The mean NR‐PM1 mass concentration was 20.94 ± 10.14 μg m−3, among which organics (47%) was the most abundant component, followed by sulfate (37%), ammonium (11%), nitrate (4%), and chloride (1%). Notably, sulfate accounted for more than 70% of the secondary inorganic aerosols. Positive matrix factorization (PMF) analysis of the composition data resulted in three organic aerosol (OA) factors: hydrocarbon‐like OA (HOA), oxygenated OA I (OOA‐I), and oxygenated OA II (OOA‐II). The secondary organic aerosol (SOA) composed of the latter two factors (SOA: OOA‐I + OOA‐II) was dominant in OA (80.7%). The PMF analysis of the PNSD data yielded three factors: new particle formation related mode, growth mode, and accumulation mode, among which the last factor dominated both number and volume ratios. The sulfate formation was characterized by the sulfur oxidation ratio (SOR), heterogeneous sulfate production rate (Phet), and gaseous sulfuric acid concentration, representing secondary sulfate transformation, heterogeneous reactions, and gas phase reactions, respectively. The results showed that Phet was well correlated with both sulfate concentrations and SOR, especially during the polluted periods. Our study demonstrates that photochemically‐driven heterogeneous reactions contribute dominantly to the sulfate formation and SOA is formed predominantly by photochemical oxidation of volatile organic compounds under high temperatures and ultraviolet (UV) intensities, and NOX concentrations on Mt. Wudang during the campaign period.

A proxy for atmospheric daytime gaseous sulfuric acid concentration in urban Beijing

Abstract. Gaseous sulfuric acid (H2SO4) is known as one of the key precursors for atmospheric new particle formation (NPF) processes, but its measurement remains challenging. Therefore, a proxy method that is able to derive gaseous sulfuric acid concentrations from parameters that can be measured relatively easily and accurately is highly desirable for the atmospheric chemistry community. Although such methods are available for clean atmospheric environments, a proxy that works well in a polluted atmosphere, such as that found in Chinese megacities, is yet to be developed. In this study, the gaseous sulfuric acid concentration was measured in February–March 2018, in urban Beijing using a nitrate based – long time-of-flight chemical ionization mass spectrometer (LToF-CIMS). A number of atmospheric parameters were recorded concurrently including the ultraviolet radiation B (UVB) intensity, the concentrations of O3, NOx (sum of NO and NO2), SO2, and HONO, and aerosol particle number size distributions. A proxy for atmospheric daytime gaseous sulfuric acid concentration was derived via a statistical analysis method using the UVB intensity, [SO2], the condensation sink (CS), [O3], and [HONO] (or [NOx]) as the predictor variables, where square brackets denote the concentrations of the corresponding species. In this proxy method, we considered the formation of gaseous sulfuric acid from reactions of SO2 and OH radicals during the daytime, and the loss of gaseous sulfuric acid due to its condensation onto the preexisting particles. In addition, we explored the formation of OH radicals from the conventional gas-phase photochemistry using O3 as a proxy and from the photolysis of HONO using HONO (and subsequently NOx) as a proxy. Our results showed that the UVB intensity and [SO2] are dominant factors in the production of gaseous sulfuric acid, and that the simplest proxy could be constructed with the UVB intensity and [SO2] alone. When the OH radical production from both homogenously and heterogeneously formed precursors were considered, the relative errors were reduced by up to 20 %.

Model studies of volatile diesel exhaust particle formation: are organic vapours involved in nucleation and growth?

Abstract. A high concentration of volatile nucleation mode particles (NUP) formed in the atmosphere when the exhaust cools and dilutes has hazardous health effects and it impairs the visibility in urban areas. Nucleation mechanisms in diesel exhaust are only poorly understood. We performed model studies using two sectional aerosol dynamics process models AEROFOR and MAFOR on the formation of particles in the exhaust of a diesel engine, equipped with an oxidative after-treatment system and running with low fuel sulfur content (FSC) fuel, under laboratory sampling conditions where the dilution system mimics real-world conditions. Different nucleation mechanisms were tested. Based on the measured gaseous sulfuric acid (GSA) and non-volatile core and soot particle number concentrations of the raw exhaust, the model simulations showed that the best agreement between model predictions and measurements in terms of particle number size distribution was obtained by barrier-free heteromolecular homogeneous nucleation between the GSA and a semi-volatile organic vapour combined with the homogeneous nucleation of GSA alone. Major growth of the particles was predicted to occur due to the similar organic vapour at concentrations of (1−2) × 1012 cm−3. The pre-existing core and soot mode concentrations had an opposite trend on the NUP formation, and the maximum NUP formation was predicted if a diesel particle filter (DPF) was used. On the other hand, the model predicted that the NUP formation ceased if the GSA concentration in the raw exhaust was less than 1010 cm−3, which was the case when biofuel was used.

Reasearch on the Formation Mechanisms of New Particles in the Atmosphere

New particle formation (NPF) in the atmosphere i.e. nucleation of gas phase precursors and continuing condensa- tional growth is a crucial secondary transformation process. The freshly nucleated particles can grow into sizes where they can act as cloud condensation nuclei (CCN) and further influence cloud and climate-relevant properties. Hence, the detailed knowledge on the formation mechanisms of new particles and their subsequent growth will help us to improve our under- standing on the regional air pollution and global climate change. Recent-developed measurement techniques enable to ex- plore atmospheric nucleation by measuring particles/clusters down to 1 nm. NPF events have been observed in a variety of atmospheric environments. Several methods including field observation, laboratory simulations and model calculations are implemented to investigate the nucleation mechanisms and growth properties. Good agreement between particle formation rates and gaseous sulfuric acid concentrations is observed, indicating that sulfuric acid is a key compnent in the atmospheric nucleation process. In addition, the low-volatile organic vapors are found to be involved in new particle formation. However, the huge variations of the particle formation and growth rates in diverse atmospheric environments suggest that a consistent picture on formation mechanisms of new particles does not achieve. Long-term continuous measurements of NPF events have been first performed in the urban atmosphere of Beijing since 2004. Up to now, NPF events have been observed in many different environments, including coastal area, high-elevation mountain, rural site as well as urban region in China. The cur- rent nucleation mechanisms are developed based on the observation in clean environment. Hence, whether it could well ex- plain the NPF events occurred in the polluted atmosphere with strong oxidation capacity is a key issue to be addressed in further studies. This paper reviews the measurement techniques for investigating atmospheric new particle formation and growth, summarizes the observation results in various typical environments, introduces the current understanding of the nu- cleation mechanisms and discusses the main scientific questions that need further researches. Keywords new particle formation; nucleation mechanism; growth property; measurement technique; precursor 1 引言

First Online Measurements of Sulfuric Acid Gas in Modern Heavy-Duty Diesel Engine Exhaust: Implications for Nanoparticle Formation

To mitigate the diesel particle pollution problem, diesel vehicles are fitted with modern exhaust after-treatment systems (ATS), which efficiently remove engine-generated primary particles (soot and ash) and gaseous hydrocarbons. Unfortunately, ATS can promote formation of low-vapor-pressure gases, which may undergo nucleation and condensation leading to formation of nucleation particles (NUP). The chemical nature and formation mechanism of these particles are only poorly explored. Using a novel mass spectrometric method, online measurements of low-vapor-pressure gases were performed for exhaust of a modern heavy-duty diesel engine operated with modern ATS and combusting low and ultralow sulfur fuels and also biofuel. It was observed that the gaseous sulfuric acid (GSA) concentration varied strongly, although engine operation was stable. However, the exhaust GSA was observed to be affected by fuel sulfur level, exhaust after-treatment, and driving conditions. Significant GSA concentrations were measured also when biofuel was used, indicating that GSA can be originated also from lubricant oil sulfur. Furthermore, accompanying NUP measurements and NUP model simulations were performed. We found that the exhaust GSA promotes NUP formation, but also organic (acidic) precursor gases can have a role. The model results indicate that that the measured GSA concentration alone is not high enough to grow the particles to the detected sizes.

Calibration of a Chemical Ionization Mass Spectrometer for the Measurement of Gaseous Sulfuric Acid

The accurate measurement of the gaseous sulfuric acid concentration is crucial within many fields of atmospheric science. Instruments utilizing chemical ionization mass spectrometry (CIMS) measuring H(2)SO(4), therefore, require a careful calibration. We have set up a calibration source that can provide a stable and adjustable concentration of H(2)SO(4). The calibration system initiates the production of sulfuric acid through the oxidation of SO(2) by OH. The hydroxyl radical is produced by UV photolysis of water vapor. A numerical model calculates the H(2)SO(4) concentration provided at the outlet of the calibration source. From comparison of this concentration and the signals measured by CIMS, a calibration factor is derived. This factor is evaluated to be 1.1 × 10(10) cm(-3), which is in good agreement with values found in the literature for other CIMS instruments measuring H(2)SO(4). The calibration system is described in detail and the results are discussed. Because the setup is external to the CIMS instrument, it offers the possibility for future CIMS intercomparison measurements by providing defined and stable concentrations of sulfuric acid.

Evaluation on the role of sulfuric acid in the mechanisms of new particle formation for Beijing case

Abstract. New particle formation (NPF) is considered as an important mechanism for gas-to-particle transformation, and gaseous sulfuric acid is believed as a crucial precursor. Up to now few field-based studies on nucleation mechanisms and the role of sulfuric acid were conducted in China. In this study, simultaneously measurements of particle number size distributions and gaseous sulfuric acid concentrations were performed from July to September in 2008. Totally, 22 new particle formation events were observed during the entire 85 campaign days. The results show that in the case of both higher source and sink values, the result of the competition between source and sink is more likely the key limiting factor to determine the observation of NPF events in Beijing. The concentrations of gaseous sulfuric acid show good correlations with freshly nucleated particles (N3-6 and formation rates (J3 and J1.5. The power-law relationship between H2SO4 concentration and N3-6 or J is adopted to explore the nucleation mechanism. The exponents are showed a great range (from 1 to 7). More than half of the NPF events exhibit an exponent larger than 2.5. For these cases, the thermodynamic process works better than the activation or kinetic nucleation theories to explain the nucleation events in urban atmosphere of Beijing.

How biogenic terpenes govern the correlation between sulfuric acid concentrations and new particle formation

New particle formation has been observed to take place all around the world. However, because of the inability to determine the chemical composition of the smallest clusters or particles, indirect tools such as the correlation between nucleation rate and measured sulfuric acid concentrations have been used to infer the nucleation mechanism. In this study we describe the observed correlation with gaseous sulfuric acid concentrations by interactions of sesquiterpene oxidation products with sulfuric acid. Two formation pathways of nucleation initiating molecules are considered. The interaction of sulfuric acid with organic sulfates, which are formed from stabilized Criegee intermediates (sCIs, formed from sesquiterpenes), can be used to explain the observed squared relationship between particle formation rate and ambient sulfuric acid concentrations. The corresponding linear dependence is explained with the participation of secondary ozonides, which are formed from sCIs and aldehydes. Both pathways are negatively affected by increasing water vapor concentration as observed in recent studies. In order to check the assumptions made we apply the derived nucleation coefficients to measurements of the BACCI/QUEST IV campaign made during spring 2005 in Hyytiälä, Finland. A reasonable agreement between the measurement data and the predicted nucleation rates is found, giving support for the presented nucleation description.

The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales

Abstract. The contribution of boundary layer (BL) nucleation events to total particle concentrations on the global scale has been studied by including a new particle formation mechanism in a global aerosol microphysics model. The mechanism is based on an analysis of extensive observations of particle formation in the BL at a continental surface site. It assumes that molecular clusters form at a rate proportional to the gaseous sulfuric acid concentration to the power of 1. The formation rate of 3 nm diameter observable particles is controlled by the cluster formation rate and the existing particle surface area, which acts to scavenge condensable gases and clusters during growth. Modelled sulfuric acid vapour concentrations, particle formation rates, growth rates, coagulation loss rates, peak particle concentrations, and the daily timing of events in the global model agree well with observations made during a 22-day period of March 2003 at the SMEAR II station in Hyytiälä, Finland. The nucleation bursts produce total particle concentrations (>3 nm diameter) often exceeding 104 cm−3, which are sustained for a period of several hours around local midday. The predicted global distribution of particle formation events broadly agrees with what is expected from available observations. Over relatively clean remote continental locations formation events can sustain mean total particle concentrations up to a factor of 8 greater than those resulting from anthropogenic sources of primary organic and black carbon particles. However, in polluted continental regions anthropogenic primary particles dominate particle number and formation events lead to smaller enhancements of up to a factor of 2. Our results therefore suggest that particle concentrations in remote continental regions are dominated by nucleated particles while concentrations in polluted continental regions are dominated by primary particles. The effect of BL particle formation over tropical regions and the Amazon is negligible. These first global particle formation simulations reveal some interesting sensitivities. We show, for example, that significant reductions in primary particle emissions may lead to an increase in total particle concentration because of the coupling between particle surface area and the rate of new particle formation. This result suggests that changes in emissions may have a complicated effect on global and regional aerosol properties. Overall, our results show that new particle formation is a significant component of the aerosol particle number budget.

First gaseous ion composition measurements in the exhaust plume of a jet aircraft in flight: Implications for gaseous sulfuric acid, aerosols, and chemiions

Mass spectrometric composition measurements of gaseous negative ions have been made in the exhaust plume of a commercial jet aircraft (Airbus A310) in flight at altitudes around 10.4 km and at two plume ages around 3.0 and 3.6 s. Negative ions observed inside the exhaust plume are mostly NO3−(HNO3)m and HSO4−(HNO3)m with m ≤2. Outside the plume in the “background” atmosphere the same negative ion species with the same R = (HSO4−(HNO3)m)/(NO3−(HNO3)m) were observed. This indicates that the ions observed in the plume were entrained ambient atmospheric ions. By contrast no indications for negative chemiions (with masses ≤1100 amu) produced by the airbus engines were found in the plume. Furthermore our measurements indicate a modest decrease of the total concentration of entrained negative ions in the plume compared to the ambient atmosphere outside the plume. This decrease may be due to ion‐removal by ion‐attachment to aerosol‐particles and/or ion‐recombination with positive chemiions. We propose that the observed entrained ions can serve as probes for important plume components including gaseous sulfuric acid, aerosol particles and chemiions. Making use of this analytical potential we infer upper limits for the gaseous sulfuric acid concentration, total aerosol surface area density, and positive chemiion concentration. We conclude that initially formed gaseous sulfuric acid must have experienced rapid gas‐to‐particle conversion already in the very early plume at plume ages < 1.6 s.

First composition measurements of stratospheric negative ions and inferred gaseous sulfuric acid in the winter Arctic vortex: Implications for aerosols and hydroxyl radical formation

Negative ion composition measurements and inferred gaseous sulfuric acid concentrations were for the first time obtained in the winter arctic vortex. The observations were made by a balloon‐borne quadrupole mass spectrometer, between 24 and 30 km altitude, on 18 January 1992. The H2SO4 data provide strong evidence for an additional OH source, other than photochemical OH‐production from O(¹D), operative in the winter arctic stratosphere. The additional OH source might be due to ion‐molecule reactions involving ambient ions, formed by galactic cosmic rays. This mechanism seems to explain the presence of gaseous sulfuric acid in the winter arctic vortex and may even influence H2SO4 abundances at midlatitudes during nighttime.