Formation and growth of indoor air aerosol particles as a result of d-limonene oxidation

Oxidation of d-limonene, which is a common monoterpene, can lead to new aerosol particle formation in indoor environments. Thus, products containing d-limonene, such as citrus fruits, air refresheners, household cleaning agents, and waxes, can act as indoor air aerosol particle sources. We released d-limonene into the room air by peeling oranges and measured the concentration of aerosol particles of three different size ranges. In addition, we measured the concentration of d-limonene, the oxidant, and the concentration of ozone, the oxidizing gas. Based on the measurements we calculated the growth rate of the small aerosol particles, which were 3–10 nm in diameter, to be about , and the losses of the aerosol particles that were due to the coagulation and condensation processes. From these, we further approximated the concentration of the condensable vapour and its source rate and then calculated the formation rate of the small aerosol particles. For the final result, we calculated the nucleation rate and the maximum number of molecules in a critical cluster. The nucleation rate was in the order of and the number of molecules in a critical-sized cluster became 1.2. The results were in agreement with the activation theory.     

A theoretical study of hydrogen-bonded molecular clusters of sulfuric acid and organic acids with amides

Amides, a series of significant atmospheric nitrogen-containing volatile organic compounds (VOCs), can participate in new particle formation (NPF) throught interacting with sulfuric acid (SA) and organic acids. In this study, we investigated the molecular interactions of formamide (FA), acetamide (AA), N-methylformamide (MF), propanamide (PA), N-methylacetamide (MA), and N,N-dimethylformamide (DMF) with SA, acetic acid (HAC), propanoic acid (PAC), oxalic acid (OA), and malonic acid (MOA). Global minimum of clusters were obtained through the association of the artificial bee colony (ABC) algorithm and density functional theory (DFT) calculations. The conformational analysis, thermochemical analysis, frequency analysis, and topological analysis were conducted to determine the interactions of hydrogen-bonded molecular clusters. The heterodimers formed a hepta or octa membered ring through four different types of hydrogen bonds, and the strength of the bonds are ranked in the following order: SOH???O > COH???O > NH???O > CH???O. We also evaluated the stability of the clusters and found that the stabilization effect of amides with SA is weaker than that of amines with SA but stronger than that of ammonia (NH₃) with SA in the dimer formation of nucleation process. Additionally, the nucleation capacity of SA with amides is greater than that of organic acids with amides.     

Experimental investigation of the flow characteristics of jettisoning in a CO2 carrier

This experimental study was performed to investigate the flow characteristics in the jettisoning flow line of a liquid CO₂ carrier. When a pressurized liquid CO₂ container loses mechanical integrity, possibly by material or mechanical defects, the liquid inventory should be drained out rapidly for safety reasons using the so-called jettisoning process. In the course of jettisoning, the liquid CO₂ undergoes two phase change stages, from liquid to liquid + vapor and from liquid + vapor to solid + vapor. Consequently, the jettisoning release rate is affected by the characteristics of these phase changes. In this study, liquid CO₂ was discharged through a small tube, representing a jettisoning flow line. The temperature and pressure were measured along the tube, and the locations of the phase changes were inferred from the measured data. The experimental results showed that active nucleation occurred near the tube tip and that the phase change into solid and vapor occurred just after leaving the pipe, irrespective of the tube length in this study.     

Thermal volatilization properties of atmospheric nanoparticles

Thermal volatilization is explored as a means of inferring the chemical composition of atmospheric aerosol particles with diameters smaller than 10 nm (nanoparticles). Such particles contain too little mass for quantitative chemical determination by traditional analytical methods. Aerosols were subjected to increasing temperature in an oven and particle loss was measured as a function of temperature with the TSI model 3025 ultrafine condensation particle counter (UCPC), which is capable of counting particles with diameters as small as 3 nm. Particle nucleation was observed down stream of the oven when it was heated above about 400°C. To reduce this artifact, the sample air down stream of the oven was cooled to condense the hot gases and/or the freshly nucleated particles before they reached the UCPC. Controlled experiments were done with pure ammonium sulfate (NH₄)₂SO₄ particles. The experimental design was optimized based on the known concentration of pure (NH₄)₂SO₄ particles vaporized in the oven and the diffusion of this material to the walls of the sampling tube before the particle counter.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of >10 nm new particles.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of > 10 nm new particles.     

Interactions of sulfuric acid with common atmospheric bases and organic acids: Thermodynamics and implications to new particle formation

Interactions of the three common atmospheric bases, dimethylamine ((CH₃)₂NH), methylamine (CH₃NH₂), ammonia (NH₃), all considered to be efficient stabilizers of binary clusters in the Earth's atmosphere, with H₂SO₄, the key atmospheric precursor, and 14 common atmospheric organic acids (COAs) (formic, acetic, oxalic, malonic, succinic, glutaric acid, adipic, benzoic, phenylacetic, pyruvic, maleic acid, malic, tartaric and pinonic acids) have been studied using the density functional theory (DFT) and composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA)(H₂SO₄), (COA)(B1), (COA)(B2) and (COA)(B3) dimers and (COA)(H₂SO₄)(B1), (COA)(H₂SO₄)(B2) and (COA)(H₂SO₄)(B3) trimers, where B1, B2 and B3 refer to (CH₃)₂NH, CH₃NH₂ and NH₃, respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H₂SO₄ have been studied. Our investigation shows that interactions of H₂SO₄ with COA, (CH₃)₂NH, CH₃NH₂ and NH₃ lead to the formation of more stable mixed dimers and trimers than (H₂SO₄)₂ and (H₂SO₄)₂(base), respectively, and emphasize the importance of common organic species for early stages of atmospheric nucleation. We also show that although amines are generally confirmed to be more active than NH₃ as stabilizers of binary clusters, in some cases mixed trimers containing NH₃ are more stable thermodynamically than those containing CH₃NH₂. This study indicates an important role of COA, which coexist and interact with that H₂SO₄ and common atmospheric bases in the Earth atmosphere, in formation of stable pre-nucleation clusters and suggests that the impacts of COA on new particle formation (NPF) should be studied in further details.