H2SO4 Formation Research Articles

Effect of industrial alkene ozonolysis on atmospheric H2SO4 formation

This study has employed the master chemical mechanism (MCM) to investigate the influence of the ozone oxidation pathways in the atmospheric formation of H2SO4 from short-chain olefins in industrialized areas. In-situ H2SO4 formation data were obtained using a high-resolution chemical ionization time-of-flight mass spectrometer, and the simulated H2SO4 concentrations calculated using updated parameters for the MCM model exhibited good agreement with observations. In the simulation analysis of different reaction pathways involved in H2SO4 formation, hydroxyl radicals were found to dominate H2SO4 production during the daytime, while olefin ozone oxidation contributed up to 65% of total H2SO4 production during the night-time. A sensitivity analysis of the H2SO4 production parameters has revealed a high sensitivity to changes in sulfur dioxide, and a relatively high sensitivity to olefins with fast ozonolysis reaction rates and bimolecular reaction rates of resulting stabilized Criegee Intermediates. A high relative humidity promotes daytime H2SO4 formation, but has an inhibiting effect during the night-time due to the different dominant reaction pathways.

Determination of the influence of water on the SO3 + CH3OH reaction in the gas phase and at the air-water interface.

Liu et al. (Proc. Natl. Acad. Sci. U. S. A, 2019, 116, 24966-24971) showed that at an altitude of 0 km, the reaction of SO3 with CH3OH to form CH3OSO3H reduces the amount of H2SO4 produced by the hydrolysis of SO3 in regions polluted with CH3OH. However, the influence of the water molecule has not been fully considered yet, which will limit the accuracy of calculating the loss of SO3 in regions polluted with CH3OH. Here, the influence of water molecules on the SO3 + CH3OH reaction in the gas phase and at the air-water interface was comprehensively explored by using high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations. Quantum chemical calculations show that both pathways for the formation of CH3OSO3H and H2SO4 with water molecules have greatly lowered energy barriers compared to the naked SO3 + CH3OH reaction. The effective rate coefficients reveal that H2O-catalyzed CH3OSO3H formation (a favorable route for CH3OSO3H formation) can be competitive with H2O-assisted H2SO4 formation (a favorable process for H2SO4 formation) at high altitudes up to 15 km. BOMD simulations found that H2O-induced formation of the CH3OSO3-⋯H3O+ ion pair and CH3OH-assisted formation of HSO4- and H3O+ ions were observed at the droplet surface. These interfacial routes followed a loop-structure or chain reaction mechanism and proceeded on a picosecond time scale. These results will contribute to better understanding of SO3 losses in the polluted areas of CH3OH.

Photochemistry of HOSO2 and SO3 and Implications for the Production of Sulfuric Acid.

Sulfur trioxide (SO3) and the hydroxysulfonyl radical (HOSO2) are two key intermediates in the production of sulfuric acid (H2SO4) on Earth's atmosphere, one of the major components of acid rain. Here, the photochemical properties of these species are determined by means of high-level quantum chemical methodologies, and the potential impact of their light-induced reactivity is assessed within the context of the conventional acid rain generation mechanism. Results reveal that the photodissociation of HOSO2 occurs primarily in the stratosphere through the ejection of hydroxyl radicals (•OH) and sulfur dioxide (SO2). This may decrease the production rate of H2SO4 in atmospheric regions with low O2 concentration. In contrast, the photostability of SO3 under stratospheric conditions suggests that its removal efficiency, still poorly understood, is key to assess the H2SO4 formation in the upper atmosphere.

Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

Abstract. Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

Impact of air contamination by NOx on the performance of high temperature PEM fuel cells

High temperature PEM fuel cells show enhanced tolerances regarding fuel impurities like CO for use in various applications. However, the impact of air impurities like NOx on the cell behavior is not completely understood yet. This study provides systematic investigation during 500 h of operation in presence of cathode air containing 10 ppm NO or NO2. Nitrogen oxides provoke a strongly and linearly decreasing voltage of 245.3 ± 18.5 μV h−1 and highly comparable damage that verifies similar HT-PEMFC degradation via both oxides. Cyclic voltammetry and electron microscopy reveal the loss of electrochemical catalyst surface by selectively poisoned surface and enforced catalyst particle growth. Impedance spectroscopy reveals besides increased electrode charge transfer resistances an affected proton conductivity. In contrast, SO2/NO2 impurity mixture in real occurring ratio causes less voltage decay due to a positive SO2 impact through H2SO4 formation causing further shown and discussed effects like nitrate formation and discharge.

Unprecedented Ambient Sulfur Trioxide (SO3) Detection: Possible Formation Mechanism and Atmospheric Implications.

Sulfur trioxide (SO3) is a crucial compound for atmospheric sulfuric acid (H2SO4) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO3 is mainly produced from the photo-oxidation of SO2 by OH radicals. However, the sources of SO3 during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-of-flight) mass spectrometer to detect atmospheric SO3 and H2SO4. Our results show the level of SO3 was higher during the winter than during the summer, with high SO3 levels observed especially during the early morning (∼05:00 to ∼08:30) and night (∼18:00 to ∼05:00 the next day). On the basis of analysis of SO2, NOx, black carbon, traffic flow, and atmospheric ions, we suggest SO3 could be formed from the catalytic oxidation of SO2 on the surface of traffic-related black carbon. This previously unidentified SO3 source results in significant H2SO4 formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO3 and formulating policies to mitigate secondary particle formation in Chinese megacities.

Biocorrosion of Concrete Sewers in Greece: Current Practices and Challenges

This paper is intended to review the current practices and challenges regarding the corrosion of the Greek sewer systems with an emphasis on biocorrosion and to provide recommendations to avoid it. The authors followed a holistic approach, which included survey data obtained by local authorities serving more than 50% of the total country’s population and validated the survey answers with field measurements and analyses. The exact nature and extent of concrete biocorrosion problems in Greece are presented for the first time. Moreover, the overall condition of the sewer network, the maintenance frequency, and the corrosion prevention techniques used in Greece are also presented. Results from field measurements showed the existence of H2S in the gaseous phase (i.e., precursor of the H2SO4 formation in the sewer) and acidithiobacillus bacteria (i.e., biocorrosion causative agent) in the slime, which exists at the interlayer between the concrete wall and the sewage. Biocorrosion seems to mainly affect old concrete networks, and the replacement of the destroyed concrete pipes with new polyvinyl chloride (PVC) ones is currently common practice. However, in most cases, the replacement cost is high, and the authors provide some recommendations to increase the current service life of concrete pipes.

Acidithiobacillus thiooxidans IW16 and Sulfur Synergistically with Struvite Aggrandize the Phosphorus Bioavailability to Wheat in Alkaline Soil

Environmentally hazardous wastewaters from various origins could prove an impending source for phosphorus (P) recovery as struvite. This study aimed to employ an eco-friendly approach for P utilization from struvite, and to neutralize its alkaline effect in the soil through supplementation of sulfur-oxidizing bacteria (SOB) Acidithiobacillus thiooxidans IW16. Struvite precipitated and recovered from wastewater was tested for P release and bioavailability to grow wheat in alkaline soil under greenhouse conditions. Treatments were control (no P application), P from single superphosphate (SSP) fertilizer, P from struvite, P from struvite + sulfur (100 mg kg−1 of soil), and P from rock phosphate; and all these treatments were compared with and without SOB inoculation through irrigation water. Struvite application, especially with sulfur and/or SOB, maintained an adequate P level (as with SSP fertilizer) in both wheat plants and soil throughout the growing period. Wheat plant agronomic attributes were also improved with struvite as for SSP fertilization. Moreover, supplementation of SOB inoculum with struvite and other P sources significantly improved the P bioavailability and crop yield through increased phosphate solubility in alkaline soil. In conclusion, inoculation of SOB especially with sulfur (S) supplementation in struvite treatment caused the pH reduction of alkaline soil through S oxidation (H2SO4 formation), which solubilized the fixed-P in struvite as well as soil and thus improved P bioavailability to wheat plants. These findings strengthen the concept of struvite scavenging from wastewater for environmental safety, and to introduce it as an alternative resource for P fertilization.

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SOx with H2O and H2S.

We have performed an extensive computational investigation of the potential energy surfaces for the reactions of SOx (x = 2 or 3) with H2S and H2O in the gas phase and in aqueous solution at the CCSD(T)/CBS level of theory plus a self-consistent reaction field approach. Formation of a gas-phase H2SO4 from the hydrolysis of SO3 at lower temperatures requires the presence of additional water molecules. When additional waters are introduced, the barrier for H2SO4 formation is significantly reduced, and a barrierless transition occurs with only three excess waters as well as in aqueous solution. In a mixture of H2O, H2S, and SO3, formation of H2S2O3 has a lower barrier in the gas phase than does the formation of H2SO4. In aqueous solution, no barrier is predicted, and both are likely to be formed. Introduction of an additional water to the SO3 + H2S reaction results in a decrease in barrier height, nearly identical to the ∼18 kcal/mol catalytic effect of the first additional water in SO3 hydrolysis, with the barrier for H2S2O3 formation disappearing altogether in aqueous solution. Formation of H2SO3 by the way of SO2 hydrolysis is unlikely. Excess waters reduce the barrier for SO2 hydrolysis; however, the overall endothermicity is increased as waters are added. The formation of H2S2O2 from SO2 and H2S via an isostructural pathway to SO2 hydrolysis is unlikely, with additional water molecules resulting in a small increase in the overall endothermicity and a catalytic effect smaller than that observed for the SO3 reactions. The results of this work have implications pertaining to the formation of H2SO4, H2S2O3, H2SO3, and H2S2O2 in the atmospheres of Earth and Venus. These results also question the existence of H2S2O2 as an intermediate in the Claus process.

Impacts of SO2, Relative Humidity, and Seed Acidity on Secondary Organic Aerosol Formation in the Ozonolysis of Butyl Vinyl Ether.

Alkyl vinyl ethers are widely used as fuel additives. Despite this, their atmospheric chemistry and secondary organic aerosol (SOA) formation potentials are still not well-known under complex pollution conditions. In this work, we examined the impact of SO2, relative humidity (RH), and particle acidity on the formation and oxidation state (OSc) of SOA from butyl vinyl ether (BVE) ozonolysis. Increasing SO2 concentration produced a notable promotion of SOA formation and OSc due to the significant increase in H2SO4 particles and formation of more highly oxidized components. Increased RH in the presence of SO2 appeared to promote, suppress, and dominate the formation and OSc of SOA in the dry range (1-10%), low RH range (10-42%), and moderate RH range (42-64%), respectively. This highlights the importance of competition between H2O and SO2 in reacting with the stabilized Criegee intermediate in BVE ozonolysis at ambient RH. Increased particle acidity mainly contributed to the change in chemical composition of BVE-dominated SOA but not to SOA formation. The results presented here extend previous analysis of BVE-derived SOA and further aid our understanding of SOA formation potential of BVE ozonolysis under highly complex pollution conditions.

Leaching of yttrium, europium and accompanying elements from phosphor coatings

The aim of this work was to study and describe leaching behaviour of Y, Eu and accompanying elements (Zn, Cd) from the phosphors of waste cathode ray tube (CRT) screens in low concentrated sulphuric acid solutions under both non-oxidizing and oxidizing conditions (H2O2). Thermodynamic study showed that non-oxidizing acid leaching leads to elemental sulphur and hydrogen generation followed by formation of H2S(g). In the presence of oxidant in the leaching system SO2(g) or H2SO4 formation is possible. PbSO4 was formed during leaching independently from the presence of the oxidant. Y, Eu and Zn dissolution without using H2O2 in 0.4M H2SO4 at 80°C attained 6, 9 and 8% respectively. The appropriate content of H2O2 in leaching solution was determined as 3.9v/v %. The highest leaching efficiency of Y and Eu (around 90–95% after 20min) was achieved by using the leaching solution (400ml 0.4M H2SO4, 60ml 30v/v % H2O2) at 80°C and L/S ratio 23. Under these conditions Zn extraction was relatively low (20%) in comparison with Cd extraction (80%). The study also reveals that high leaching efficiency of both Y and Eu (around 90%) was achieved with even more diluted leaching solution (400ml 0.05M H2SO4, 60ml of 30v/v % H2O2) at 60°C, L/S ratio 23 after 20min of leaching. Zn and Cd extractions reached 20% and 55% respectively. Activation energy values calculated for Y and Eu leaching in the solution (400ml 0.4M H2SO4 with 60ml of 30v/v % H2O2) refer to diffusion mechanism in the range 40–80°C (Ea=14.85kJ/mol and 16.47kJ/mol respectively). In contrast, Ea values for Y and Eu leaching in the solution (400ml 1M H2SO4, 60ml of 30v/v % H2O2) suggest a mechanism change at the temperature around 40°C. The leaching of Y as well as Eu up to 40°C is controlled by diffusion and at higher temperatures by chemical reaction.

Microkinetic modeling of H2SO4 formation on Pt based diesel oxidation catalysts

The presence of water vapor and sulfur oxides in diesel engine exhaust leads to the formation of sulfuric acid (H2SO4), which severely impacts the performance of Pt/Pd based emissions aftertreatment catalysts. In this study, a microkinetic model is developed to investigate the reaction pathways of H2SO4 formation on Pt based diesel oxidation catalysts (DOCs). The microkinetic model consists of 14 elementary step reactions (7 reversible pairs) and yields prediction in excellent agreement with data obtained from experiments at practically relevant sulfur oxides environment in engine exhaust. The model simulation utilizing a steady-state plug flow reactor demonstrates that it matches experimental data in both kinetically and thermodynamically controlled regions. Results clearly show the negative impact of SO3 on the SO2 oxidation light-off temperature, consistent with experimental observations. A reaction pathway analysis shows that the primary pathway of sulfuric acid formation on Pt surface involves SO2* oxidation to form SO3* with the subsequent interaction of SO3* with H2O* to form H2SO4*.

Bio-Corrosion Resistance of Concretes Containing Antimicrobial Ground Granulated Blastfurnace Slag BIOLANOVA and Novel Hybrid H-CEMENT

The article deals with the study of biocorrosion of concretes by sulphuric acid induced by oxidizing bacteria Acidithiobacillus thiooxidans. The concretes were prepared from reference cement CEM I 42,5 N, the mixtures of CEM I 42,5 N and antimicrobial ground granulated blastfurnace slag BIOLANOVA (GGBS) (with amount of GGBS 65 mass % - CEM III/A 32,5 N, 75 mass % - CEM III/B 32,5 N, 85 mass % - CEM III/C 32,5 N a 95 mass % - CEM III/C 32,5 N) and novel hybrid cement H-CEMENT (HC). The experiments were carried out in model laboratory conditions at 30 °C during 91 days. The degree of deterioration of concrete samples has been studied on the base of the pH changes of leachate, the concentrations of selected ions such as S, Ca and Si and the mass changes. It has been clearly confirmed, that in the presence of bacteria, the pronounced degradation of the samples occurred with exception of HC sample, which behaviour proved differences to the other samples. The HC concrete possessed more alkali leachate in comparison with the others. The concentration of sulphur S in leachate was increased by metabolic activity of bacteria due to biogenic H2SO4 formation. The increase of S concentration acidified leachate and so promoted leaching next substances from the samples. The concentration of silicon Si in leachate was promoted by metabolic activity of bacteria, as well. The development of Ca leaching concentration has been similar at all composite samples as in the case of reference CEM I 42,5 N concrete, however the smallest portion of leached Ca has been determined at HC concrete. The Ca leaching concentration has been increasing with the amount of GGBS being added to the composite CEM III concretes. The different tendency has been also observed at the HC samples in regards to the mass changes. The increase in mass has been measured at all concrete samples with exception of HC concrete, at which the mass decrease has been found out. The results confirmed the resistance of the concrete composite samples containing GGBS and HC to the sulphate attack and the HC sample showed the highest resistance to the sulphate biocorrosion.

An unexpected gaseous sulfur species

Sulfur Chemistry Sulfuric acid plays a central role in both industrial and atmospheric contexts. As such, the behavior of SO3 mixtures in gas phases has been studied for over a century. In gas-phase experiments on wet SO3 and formic acid, Mackenzie et al. discovered a previously unrecognized covalent adduct: formic sulfuric anhydride, or HC(O)OSO3H. The combination of microwave spectroscopy and theoretical calculations reveals its structural properties. The compound may play a role in the nucleation of atmospheric aerosols by serving as an intermediate to H2SO4 formation. Science , this issue p. [58][1] [1]: /lookup/doi/10.1126/science.aaa9704

Missing SO<sub>2</sub> oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Abstract. Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 104 cm−3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 μm (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated H2SO4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on {ab initio} calculations. Nevertheless, IO could contribute significantly to the observed CIMS background signal. A detailed analysis of this CIMS background signal in context with recently published kinetic data currently suggests that Criegee intermediates (CIs) produced from ozonolysis of alkenes play no significant role for SO2 oxidation in the marine atmosphere at Mace Head. On the other hand, SO2 oxidation by small CIs such as CH2OO produced photolytically or possibly in the photochemical degradation of methane is consistent with our observations. In addition, H2SO4 formation from dimethyl sulfide oxidation via SO3 as an intermediate instead of SO2 also appears to be a viable explanation. Both pathways need to be further explored.

Competing atmospheric reactions of CH2OO with SO2 and water vapour.

H2SO4 formation from the reaction CH2OO + SO2 has been measured as a function of the water vapour concentration for close to atmospheric conditions. Second-order kinetics with regard to water indicates a preferred reaction of CH2OO with the water dimer. The obtained kinetic parameters lead to the conclusion that the atmospheric fate of CH2OO is dominated by the reaction with water vapour. A comparison with results from CH3CHOO and (CH3)2COO indicates a structure dependent reactivity of stabilized Criegee intermediates.

H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature

The importance of gas-phase products from alkene ozonolysis other than OH radicals, most likely stabilized Criegee Intermediates (sCI), for the process of atmospheric SO2 oxidation to H2SO4 has been recently discovered. Subjects of this work are investigations on H2SO4 formation as a function of water vapour content (RH = 2–65%) and temperature (278–343 K) starting from the ozonolysis of trans-2-butene and 2,3-dimethyl-2-butene (TME). H2SO4 production other than via the OH radical reaction was attributed to the reaction of SO2 with sCI, i.e. acetaldehyde oxide arising from trans-2-butene ozonolysis and acetone oxide from TME. Measurements have been conducted in an atmospheric pressure flow tube using NO3−–CI-APi-TOF mass spectrometry for H2SO4 detection. The sCI yields derived from H2SO4 measurements at 293 K were 0.49 ± 0.22 for acetaldehyde oxide and 0.45 ± 0.20 for acetone oxide. Our findings indicate a H2SO4 yield from sCI + SO2 of unity or close to unity. The deduced rate coefficient ratio for the reaction of sCI with H2O and SO2, k(sCI + H2O)/k(sCI + SO2), was found to be strongly dependent on the structure of the Criegee Intermediate, for acetaldehyde oxide at 293 K: (8.8 ± 0.4)·10−5 (syn- and anti-conformer in total) and for acetone oxide: <4·10−6. H2SO4 formation from sCI was pushed back with rising temperature in both reaction systems most probably due to an enhancement of sCI decomposition. The ratio k(dec)/k(sCI + SO2) increased by a factor of 34 (acetone oxide) increasing the temperature from 278 to 343 K. In the case of acetaldehyde oxide the temperature effect is less pronounced. The relevance of atmospheric H2SO4 formation via sCI + SO2 is discussed in view of its dependence on the structure of the Criegee Intermediate.

Enhancement of atmospheric H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;SO&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; / H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O nucleation: organic oxidation products versus amines

Abstract. Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research – Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107–108 molecule cm−3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm−3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm−3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107–1010 molecule cm−3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine &lt; aniline &lt; dimethylamine &lt; trimethylamine. This result supports the idea of H2SO4 cluster stabilization by amines due to strong H2SO4↔amine interactions. On the other hand, this study indicates that for organic oxidation products (in presence of the possible amine background as stated) a distinct H2SO4 / H2O nucleation enhancement can be due to increased H2SO4 formation caused by additional organic oxidant production (sCI) rather than by stabilization of H2SO4 clusters due to H2SO4↔organics interactions.

Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation

Carbonyl oxides ("Criegee intermediates"), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al, Sci, Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535, ref. 1-3). Recently it was shown that small Criegee intermediates, C.I.'s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ref. 4) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of 502 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ref. 5-7). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ref. 8). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.

Accurate computational determination of the binding energy of the SO3∙H2O complex

Reliable thermochemical data for the reaction SO3 + H2O<-->SO3 x H2O (1a) are of crucial importance for an adequate modeling of the homogeneous H2SO4 formation in the atmosphere. We report on high-level quantum chemical calculations to predict the binding energy of the SO3 x H2O complex. The electronic binding energy is accurately computed to De = 40.9+/-1.0 kJ/mol = 9.8+/-0.2 kcal/mol. By using harmonic frequencies from density functional theory calculations (B3LYP/cc-pVTZ and TPSS/def2-TZVP), zero-point and thermal energies were calculated. From these data, we estimate D0 = -Delta H(1a)0(0 K) = 7.7+/-0.5 kcal/mol and Delta H(1a)0(298 K) = -8.3+/-1.0 kcal/mol.