Secondary organic aerosol in residences: predicting its fraction of fine particle mass and determinants of formation strength

Indoor secondary organic aerosol (SOA) formation may contribute to particle concentrations within residences, but little systematic work has investigated its magnitude or the determinants of its formation. This work uses a time‐averaged modeling approach to predict the indoor SOA mass formed in residences due to the oxidation of 66 reactive organic compounds by ozone or the hydroxyl radical, parameterizing SOA formation with the aerosol mass fraction. Other organic and inorganic aerosols owing to outdoor and indoor sources were also predicted. Model inputs were represented as distributions within a Monte Carlo analysis, so that result distributions and sensitivity of results to inputs could be quantified, using a dataset developed from the study of Relationships between Indoor, Outdoor and Personal Air and other sources. SOA comprised a large amount of indoor organic and total fine particles for a subset of the results (e.g., >47% of indoor organic and >30% of fine aerosol for 10% of the modeled cases), but was often a small fraction. The sensitivity analysis revealed that SOA formation is driven by high terpene emission rates (particularly by d‐limonene) and outdoor ozone, along with low air exchange and ozone and particle deposition rates.     

Ultrafine particles generated from coloring with scented markers in the presence of ozone

High concentrations of ultrafine particles (UFPs) have been previously reported during school art activities. This is possibly due to secondary organic aerosols (SOAs) formed from reactions between ozone and volatile organic compounds emitted from art products. Four brands of markers, three scented and one unscented, were tested inside a stainless steel chamber at eight different ozone concentrations between 0 and 300 ppb. Out of the 32 tested markers, only the lemon‐ and orange‐scented markers from one brand reacted with ozone to form UFPs. Limonene, pinene, and several other terpenes were identified as ingredients of ink in SOA‐forming markers. Coloring with one lemon‐scented marker for 1 min without ozone generated on average approximately 26 ± 4 ppb of limonene inside the chamber. At 150 ppb ozone, using one lemon marker for 1 min formed on average 7.7 × 10¹⁰ particles. The particle size distribution indicated an initial mode of 15 nm which grew to 40 nm. At 50 ppb ozone and below, no significant SOA formation occurred. The number of particles formed is moderately correlated with the mass of ink used (R² = 0.68). Based on these data, scented markers are not likely a strong source of SOA under normal indoor ozone levels.     

A chamber study of secondary organic aerosol formation by limonene ozonolysis

Abstract Limonene ozonolysis was examined under conditions relevant to indoor environments in terms of temperatures, air exchange rates, and reagent concentrations. Secondary organic aerosols (SOA) produced and particle‐bound reactive oxygen species (ROS) were studied under situations when the product of the two reagent concentrations was constant, the specific concentration combinations play an important role in determining the total SOA formed. A combination of concentration ratios of ozone/limonene between 1 and 2 produce the maximum SOA concentration. The two enantiomers, R‐(+)‐limonene and S‐(?)‐limonene, were found to have similar SOA yields. The measured ROS concentrations for limonene and ozone concentrations relevant to prevailing indoor concentrations ranged from 5.2 to 14.5 nmol/m³ equivalent of H₂O₂. It was found that particle samples aged for 24 h in freezer lost a discernible fraction of the ROS compared to fresh samples. The residual ROS concentrations were around 83–97% of the values obtained from the analysis of samples immediately after collection. The ROS formed from limonene ozonolysis could be separated into three categories as short‐lived, high reactive, and volatile; semi‐volatile and relatively stable; non‐volatile and low‐reactive species based on ROS measurements under various conditions. Such chemical and physical characterization of the ROS in terms of reactivity and volatility provides useful insights into nature of ROS.

Practical Implications

A better understanding of the formation mechanism of secondary organic aerosol generated from indoor chemistry allows us to evaluate and predict the exposure under such environments. Measurements of particle‐bound ROS shed light on potential adverse health effect associated with exposure to particles.

     

The influence of ventilation on reactions among indoor pollutants: modeling and experimental observations

This study examines the influence of ventilation on chemical reactions among indoor pollutants. We have used a one compartment mass balance model to simulate unimolecular and bimolecular reactions occurring indoors. The initial modeling assumes steady-state conditions. However, at low air exchange rates, there may be insufficient time to achieve steady-state. Hence we have also modeled non steady-state scenarios. In the cases examined, the results demonstrate that the concentrations of products generated from reactions among indoor pollutants increase as the ventilation rate decreases. This is true for unimolecular and bimolecular reactions, regardless of whether the pollutants have indoor or outdoor sources. It is also true even when one of the pollutants has an outdoor concentration that displays large diurnal variations. We have supplemented the modeling studies with a series of experiments conducted in typical commercial offices. The reaction examined was that between ozone and limonene. The ozone was present as a consequence of outdoor-to-indoor transport while the limonene originated indoors. Results were obtained for low and high ventilation rates. Consistent with the modeling studies, the concentrations of monitored products were much larger at the lower ventilation rates (even though the ozone concentrations were lower). The potential for reactions among indoor pollutants to generate reactive and irritating products is an additional reason to maintain adequate ventilation in indoor environments.     

Heterogeneous reactions of ozone and D-limonene on activated carbon

If released in significant amounts, products formed by reactions between ozone (O3) and volatile organic compounds (VOCs) sorbed on activated carbon (AC) filters could degrade indoor air quality (IAQ). Heterogeneous reactions were investigated in laboratory experiments aimed at characterizing reaction products. Effluent air of AC loaded with limonene and exposed to O3 (5.8 ppm) yielded unreacted limonene (501+/-197 microg/m3), low levels of 4-acetyl-1-methylcyclohexene (AMCH) (20+/-2 microg/m3), and limonene oxides (25+/-7 microg/m3). Most of the O3-limonene products remained on the AC, and most (58%) of the limonene remained unreacted on the AC after exposure to a stoichiometric excess of O3 for 48 h. Thus, in addition to known homogenous reactions, O3-limonene reactions occur heterogeneously on AC but to a much lesser extent. However, the fate of 95% of the depleted limonene was not determined; much of the missing portion was attributed to desorption from the AC, but the formation of other secondary indoor air pollutants is possible. VOC-loaded AC air filters exposed to O3 seem unlikely, however, to constitute a significant emission source of reaction products. More studies are necessary to investigate other pollutants, effects of environmental conditions, and VOC releases from AC that may be enhanced by O3 exposure. PRACTICAL IMPLICATIONS: Reactions between ozone and certain volatile organic compounds such as limonene (a common ingredient of many consumer products) occurring on the surface of ventilation filters could impact indoor air quality if products are released in significant amounts. This study suggests that although very small amounts of limonene adsorbed on a filter will react with O3, ventilation filters are not likely to be significant sources of ozone oxidation products. More studies are needed to investigate whether ozone exposure enhances desorption of pollutants from ventilation filters and to measure the formation of formaldehyde and other products that are not easily retained by charcoal filters.     

Mass balance modeling of building recirculation rates and filtration efficiencies effects on secondary organic aerosols derived from ozone-initiated chemistry

Recirculation of conditioned air is a common practice in regions with hot and humid climate. This is due to the need to reduce sensible and latent cooling loads in buildings. However, recirculating used indoor air may influence indoor air chemical reactions and products derived from the chemistry. Example of such products is secondary organic aerosols (SOA) derived from ozone initiated indoor chemistry. This present study was conducted using mass balance model to examine the impacts of four recirculation rates on ozone (of outdoor origin) and SOA derived from the ozone initiated indoor chemistry. At steady-states, it was observed that the higher the recirculation rate, the lower the ozone and SOA concentration for all modeled scenarios. At steady-state, outdoor to indoor transport of ozone, indoor ozone and SOA concentrations were found to increase with increasing outdoor ozone levels. Increase in ventilation rate was found to increase outdoor to indoor transport of ozone and steady-state indoor ozone concentration. However, higher ventilation rate resulted in lower SOA concentration at steady-state. Increasing ozone filtration efficiency of activated carbon (AC) filter was found to be effective in reducing indoor ozone and SOA concentrations. This study is relevant to building sustainability in terms of health and comfort of building occupants.     

Influence of ozone-limonene reactions on perceived air quality

This study conducted short-term assessments of perceived air quality (PAQ) for six different realistic concentrations of ozone and limonene, separately or together, in room air. The impact of filtration and the influence of the ozone generation method were also examined. The evaluations were made in four identical 40 m3 low-polluting test offices ventilated at 1.4 h(-1) or in two identical 30 m3 stainless-steel chambers ventilated at 1.9 h(-1). Concentrations of ozone, total volatile organic compounds and size-fractionated particles were continuously monitored in each experiment. The results indicate that, for each of the six conditions, the PAQ was poorer when ozone and limonene were present together compared with when only ozone or only limonene was present. In the test offices a correlation was observed between the number of secondary organic aerosols produced by a given ozone/limonene condition and the sensory pollution load for that condition. The particles themselves do not appear to be the primary causative agents, but instead are co-varying surrogates for sensory offending gas-phase species. PRACTICAL IMPLICATIONS: Although the health consequences of long-term exposures to the products of ozone-initiated indoor chemistry remain to be determined, we judge that the sensory offending nature of selected products provides an additional reason to limit indoor ozone levels. Devices that emit ozone at significant rates should not be used indoors. Ozone-filtration of make-up air should also be beneficial in mechanically ventilated buildings located in regions that repeatedly violate outdoor ozone standards. Additionally, the use of limonene containing products should be curtailed during periods when indoor ozone levels are elevated.     

室内空气中潜在的化学反应与空气品质

探讨了室内污染物发生潜在反应的环境条件 ,分析了臭氧与室内无机物和有机物可能发生的化学反应和光化学反应 ,讨论了这些潜在的反应对室内空气品质的影响 ,提出了改善室内空气品质的途径     

Secondary organic aerosol formation initiated by α‐terpineol ozonolysis in indoor air

Secondary organic aerosol (SOA) owing to reactive organic gas (ROG) ozonolysis can be an important indoor particle source. However, SOA formation owing to ozonolysis of α‐terpineol, which is emitted by consumer product usage and reacts strongly with ozone, has not been systematically quantified. Therefore, we conducted 21 experiments to investigate the SOA formation initiated by α‐terpineol ozonolysis for high (0.84 h^?1), moderate (0.61 h^?1), and low (0.36 h^?1) air exchange rates (AER), which is the frequency with which indoor is replaced by outdoor air. α‐Terpineol concentrations of 6.39 to 226 ppb were combined with high ozone (~25 ppm) to ensure rapid and complete ozonolysis. No reactants were replenished, so SOA peaked quickly and then decreased due to AER and surface losses, and peak SOA ranged from 2.03 to 281 μg/m³ at unit density. SOA mass formation was parameterized with the aerosol mass fraction (AMF), a.k.a. the SOA yield, and AMFs ranged from 0.056 to 0.24. The AMFs strongly and positively correlated with reacted α‐terpineol, whereas they weakly and negatively correlated with higher AERs. One‐product, two‐product, and volatility basis set (VBS) models were fit to the AMF data. Predictive modeling demonstrated that α‐terpineol ozonolysis could meaningfully form SOA in indoor air.     

Effects of an ozone-generating air purifier on indoor secondary particles in three residential dwellings

The use of indoor ozone generators as air purifiers has steadily increased over the past decade. Many ozone generators are marketed to consumers for their ability to eliminate odors and microbial agents and to improve health. In addition to the harmful effects of ozone, recent studies have shown that heterogeneous and homogeneous reactions between ozone and some unsaturated hydrocarbons can be an important source of indoor secondary pollutants, including free radicals, carbonyls, carboxylic acids, and fine particles. Experiments were conducted in one apartment and two detached single-family dwellings in Austin, TX, to assess the effects of an ozone generator on indoor secondary organic aerosol concentrations in actual residential settings. Ozone was generated using a commercial ozone generator marketed as an air purifier, and particle measurements were recorded before, during, and after the release of terpenes from a pine oil-based cleaning product. Particle number concentration, ozone concentration, and air exchange rate were measured during each experiment. Particle number and mass concentrations increased when both terpenes and ozone were present at elevated levels. Experimental results indicate that ozone generators in the presence of terpene sources facilitate the growth of indoor fine particles in residential indoor atmospheres. Human exposure to secondary organic particles can be reduced by minimizing the intentional release of ozone, particularly in the presence of terpene sources. PRACTICAL IMPLICATIONS: Past studies have shown that ozone-initiated indoor chemistry can lead to elevated concentrations of fine particulate matter, but have generally been completed in controlled laboratory environments and office buildings. We explored the effects of an explicit ozone generator marketed as an air purifier on the formation of secondary organic aerosol mass in actual residential indoor settings. Results indicate significant increases in number and mass concentrations for particles <0.7 microns in diameter, particularly when an ozone generator is used in the presence of a terpene source such as a pine oil-based cleaner. These results add evidence to the potentially harmful effects of ozone generation in residential environments.     

Inactivation of particle-associated microorganisms in wastewater disinfection: modeling of ozone and chlorine reactive diffusive transport in polydispersed suspensions

Occlusion of microorganisms in wastewater particles often governs the overall performance of a disinfection system, and the associated health risks of post-disinfected effluents. Little is currently known on the penetration of chemical oxidants into particles developed in wastewater treatment. In this work, a reactive transport model that incorporates intra- and extra-particle chemical decay, radial intra-particle diffusion, mass transfer resistance at particle surfaces, and non-linear reaction kinetics within a competitive multi-particle size aqueous environment, was used to analyze the penetration of ozone and chlorine into wastewater particles. Individual characteristics from two secondary wastewater treatment facilities were used in model calibration. Simulations revealed that significant ozone transport within particles greater than 6 microm required large initial concentrations to exhaust the preferential reaction with aqueous soluble matter. Chlorinated samples exhibited apparently slower reactions and thus deeper penetration (22-40 microm). Chlorine penetration was less sensitive to variations in the extra-particle reaction and disinfectant concentration than ozone. Model simulations that considered elevated initial concentrations of chemical disinfectants revealed that complete inactivation of all particle size domains was not possible with current disinfection practices (e.g., contact times). Reduction in the health risks associated with wastewater particles requires treatment that efficiently balances particle removal (filtration) and particle inactivation (disinfection).     

Predicting secondary organic aerosol formation from terpenoid ozonolysis with varying yields in indoor environments

The ozonolysis of terpenoids generates secondary organic aerosol (SOA) indoors. Models of varying complexity have been used to predict indoor SOA formation, and many models use the SOA yield, which is the ratio of the mass of produced SOA and the mass of consumed reactive organic gas. For indoor simulations, the SOA yield has been assumed as a constant, even though it depends on the concentration of organic particles in the air, including any formed SOA. We developed two indoor SOA formation models for single terpenoid ozonolysis, with yields that vary with the organic particle concentration. The models have their own strengths and were in agreement with published experiments for d-limonene ozonolysis. Monte Carlo analyses were performed, which simulated different residential and office environments to estimate ranges of SOA concentrations and yields for d-limonene and α-pinene ozonolysis occurring indoors. Results indicate that yields are highly variable indoors and are most influenced by background organic particles for steady-state formation and indoor ozone concentration for transient peak formation. Additionally, a review of ozonolysis yields for indoor-relevant terpenoids in the literature revealed much uncertainty in their values at low concentrations typical of indoors. PRACTICAL IMPLICATIONS: The results in this study suggest important factors that govern indoor secondary organic aerosol (SOA) formation and yields, in typical residential and office spaces. This knowledge informs the development and comparison of control strategies to reduce indoor-generated SOA. The ranges of SOA concentrations predicted indoors allow the quantification of the effects of sorptive interactions of semi-volatile organic compounds or reactive oxygen species with SOA, filter loading owing to SOA formation, and impacts of SOA on health, if links are established.     

Atmospheric particle evolution during a nighttime atmospheric mercury depletion event in sub-Arctic at Kuujjuarapik/Whapmagoostui, Québec, Canada

During a field experiment at Kuujjuarapik/Whapmagoostui (55.31 degrees N, 77.75 degrees W), Quebec, we observed increases of concentrations of particles with diameters larger than 0.3 microm in the ambient air during a nighttime atmospheric mercury depletion event (AMDE). These increases were strongly correlated with decreases of ozone and atmospheric mercury, and we also observed a change in the particle size distribution during this AMDE. Assuming that these phenomena imply either a chemical link or an association through transport, we also studied the nature of this AMDE. We hypothesize that the observed AMDE was a result of an influx of already depleted air masses and that it was not a product of local chemical reactions.     

柔性有机堵料热解特性及产物研究

利用热重红外（TG-FTIR）联用技术,通过改变升温速率、粒径大小和气氛等条件,对柔性有机堵料的热解特性进行研究。结果表明,升温速率越慢,热解反应速率越快;较小的颗粒直径更有利于热解反应;在空气气氛下热解烟气中以CO2为主,主要由柔性有机堵料中树脂类物质发生C-O键断裂碳化反应以及无机成分分解产生。热解的冷凝液体成分中含有甲苯、苯并芘、吡啶和喹啉等多种芳香类化合物。热解后的固体残渣进行扫描电镜（SEM）、X射线衍射（XRD）和红外光谱（FTIR）分析,结果表明高温对柔性有机堵料的理化性能产生一定影响。     

Indoor air quality for chemical and ultrafine particle contaminants from printers

There are various emission sources of chemical contaminants, such as volatile organic compounds (VOCs) and ozone and particulate matter. This report is a study into the indoor air of a room containing either a laser printer/ink-jet printer, and the air contaminations were monitored for VOCs, ozone and ultrafine particle. The result confirmed an increase in the concentration of ozone and ultrafine particle numbers in the printing processes of the printer. The emission of VOCs and ozone were measured by the use of a test chamber. The chamber concentrations of styrene, xylenes and ozone were increased in printing process of the laser printer, and pentanol was detected from the ink-jet printer. The results suggest that an office or residential printer may be a source of indoor air contamination. It is necessary for emission from printers to monitor not only VOCs and particle but also ultrafine particles and other contaminants in indoor air.     

Ozone in indoor environments: concentration and chemistry

The concentration of indoor ozone depends on a number of factors, including the outdoor ozone concentration, air exchange rates, indoor emission rates, surface removal rates, and reactions between ozone and other chemicals in the air. Outdoor ozone concentrations often display strong diurnal variations, and this adds a dynamic excitation to the transport and chemical mechanisms at play. Hence, indoor ozone concentrations can vary significantly from hour-to-hour, day-to-day, and season-to-season, as well as from room-to-room and structure-to-structure. Under normal conditions, the half-life of ozone indoors is between 7 and 10 min and is determined primarily by surface removal and air exchange. Although reactions between ozone and most other indoor pollutants are thermodynamically favorable, in the majority of cases they are quite slow. Rate constants for reactions of ozone with the more commonly identified indoor pollutants are summarized in this article. They show that only a small fraction of the reactions occur at a rate fast enough to compete with air exchange, assuming typical indoor ozone concentrations. In the case of organic compounds, the "fast" reactions involve compounds with unsaturated carbon-carbon bonds. Although such compounds typically comprise less than 10% of indoor pollutants, their reactions with ozone have the potential to be quite significant as sources of indoor free radicals and multifunctional (-C=O, -COOH, -OH) stable compounds that are often quite odorous. The stable compounds are present as both gas phase and condensed phase species, with the latter contributing to the overall concentration of indoor submicron particles. Indeed, ozone/alkene reactions provide a link between outdoor ozone, outdoor particles and indoor particles. Indoor ozone and the products derived from reactions initiated by indoor ozone are potentially damaging to both human health and materials; more detailed explication of these impacts is an area of active investigation.     

Modeling of the production of secondary gaseous products in confined atmospheres

Confined environments are indoor spaces in which the air is not renewed or very poorly renewed by fresh outdoor air (spacecraft, submarines, etc.). In these environments, indoor air quality (IAQ) is expected to be highly influenced by homogeneous and heterogeneous chemistry. This paper presents a representative example of the contribution of these two phenomena to the production of secondary gaseous pollutants indoors by analyzing the chemical degradation of isoprene. An indoor air quality model was developed in the Matlab environment to compute the concentrations of both organic and nonorganic gaseous species involved in this mechanism. Two kinds of initial conditions (concentrations of nitrogen oxides, ozone and isoprene) were considered for the simulations. The results show strong interactions between homogeneous and heterogeneous reactions. Especially, the integrated reaction rate (IRR) of the heterogeneous hydrolysis of nitrogen dioxide emerges very high. Demonstration of strong interactions between inorganic and organic chemistries is also made, the conversion between NO and NO₂ being of central importance in the degradation cycle of isoprene. The type and amount of secondary products obtained are assessed. The results emphasize the strong influence of ozone and nitric oxide concentration levels indoors.     

Suppression Performance Comparison for Aspirated,Compressed-Air and In Situ Chemically Generated Class B Foams

This contribution describes the experimental program undertaken to test the performance of a novel firefighting foam against the current Class B foam technology. The novel foam involved the use of a chemical reaction between dissolved species to generate inert nitrogen gas in situ; hence in situ generated nitrogen foams (ISNF). The experimental program encompassed the utilisation of the DEF(AUST)5706 test standard for measuring the suppression and burnback performance of the ISNF as well as that of compressed air foams (CAF). All tests were performed using the same two types of surfactant concentrates (one telomer and one PFOS-based) in order to accurately determine the effect of the generation technology on the foam performance. The three kinds of foams (i.e., aspirated, CAF and ISNF) were characterised in terms of their bubble size distributions and drainage rates. Bubble size analysis placed the size distribution of the ISNF midway between those of aspirated and compressed air foams, whilst drainage performance was found to be only slightly superior to the aspirated foam. The results of the experiments showed that in situ nitrogen foams are able to achieve good performance, similar to that of aspirated and CAF technologies. Further work is needed to optimise foam formulations for ISNF so that surfactants are not affected by the chemistry of nitrogen generation and by the presence of salts formed during chemical reactions.     

Ozone reaction with clothing and its initiated VOC emissions in an environmental chamber

Human health is adversely affected by ozone and the volatile organic compounds (VOCs) produced from its reactions in the indoor environment. Hence, it is important to characterize the ozone‐initiated reactive chemistry under indoor conditions and study the influence of different factors on these reactions. This investigation studied the ozone reactions with clothing through a series of experiments conducted in an environmental chamber under various conditions. The study found that the ozone reactions with a soiled (human‐worn) T‐shirt consumed ozone and generated VOCs. The ozone removal rate and deposition velocity for the T‐shirt increased with the increasing soiling level and air change rate, decreased at high ozone concentrations, and were relatively unaffected by the humidity. The deposition velocity for the soiled T‐shirt ranged from 0.15 to 0.29 cm/s. The ozone‐initiated VOC emissions included C6–C10 straight‐chain saturated aldehydes, acetone, and 4‐OPA (4‐oxopentanal). The VOC emissions were generally higher at higher ozone, humidity, soiling of T‐shirt, and air change rate. The total molar yield was approximately 0.5 in most cases, which means that for every two moles of ozone removed by the T‐shirt surface, one mole of VOCs was produced.     

Secondary organic aerosol formation from a large number of reactive man-made organic compounds

A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential.