Cleaning products and air fresheners: emissions and resulting concentrations of glycol ethers and terpenoids

Experiments were conducted to quantify emissions and concentrations of glycol ethers and terpenoids from cleaning product and air freshener use in a 50-m3 room ventilated at approximately 0.5/h. Five cleaning products were applied full-strength (FS); three were additionally used in dilute solution. FS application of pine-oil cleaner (POC) yielded 1-h concentrations of 10-1300 microg/m3 for individual terpenoids, including alpha-terpinene (90-120), d-limonene (1000-1100), terpinolene (900-1300), and alpha-terpineol (260-700). One-hour concentrations of 2-butoxyethanol and/or d-limonene were 300-6000 microg/m3 after FS use of other products. During FS application including rinsing with sponge and wiping with towels, fractional emissions (mass volatilized/dispensed) of 2-butoxyethanol and d-limonene were 50-100% with towels retained, and approximately 25-50% when towels were removed after cleaning. Lower fractions (2-11%) resulted from dilute use. Fractional emissions of terpenes from FS use of POC were approximately 35-70% with towels retained, and 20-50% with towels removed. During floor cleaning with dilute solution of POC, 7-12% of dispensed terpenes were emitted. Terpene alcohols were emitted at lower fractions: 7-30% (FS, towels retained), 2-9% (FS, towels removed), and 2-5% (dilute). During air-freshener use, d-limonene, dihydromyrcenol, linalool, linalyl acetate, and beta-citronellol) were emitted at 35-180 mg/day over 3 days while air concentrations averaged 30-160 microg/m3. PRACTICAL IMPLICATIONS: While effective cleaning can improve the healthfulness of indoor environments, this work shows that use of some consumer cleaning agents can yield high levels of volatile organic compounds, including glycol ethers--which are regulated toxic air contaminants--and terpenes that can react with ozone to form a variety of secondary pollutants including formaldehyde and ultrafine particles. Persons involved in cleaning, especially those who clean occupationally or often, might encounter excessive exposures to these pollutants owing to cleaning product emissions. Mitigation options include screening of product ingredients and increased ventilation during and after cleaning. Certain practices, such as the use of some products in dilute solution vs. full-strength and the prompt removal of cleaning supplies from occupied spaces, can reduce emissions and exposures to 2-butoxyethanol and other volatile constituents. Also, it may be prudent to limit use of products containing ozone-reactive constituents when indoor ozone concentrations are elevated either because of high ambient ozone levels or because of the indoor use of ozone-generating equipment.     

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.     

Field‐to‐laboratory analysis of clay wall coatings as passive removal materials for ozone in buildings

Ozone reacts readily with many indoor materials, as well as with compounds in indoor air. These reactions lead to lower indoor than outdoor ozone concentrations when outdoor air is the major contributor to indoor ozone. However, the products of indoor ozone reactions may be irritating or harmful to building occupants. While active technologies exist to reduce indoor ozone concentrations (i.e, in‐duct filtration using activated carbon), they can be cost‐prohibitive for some and/or infeasible for dwellings that do not have heating, ventilating, and air‐conditioning systems. In this study, the potential for passive reduction of indoor ozone by two different clay‐based interior surface coatings was explored. These coatings were exposed to occupied residential indoor environments and tested bimonthly in environmental chambers for quantification of ozone reaction probabilities and reaction product emission rates over a 6‐month period. Results indicate that clay‐based coatings may be effective as passive removal materials, with relatively low by‐product emission rates that decay rapidly within 2 months.     

The effect of an ion generator on indoor air quality in a residential room

Ion generators charge particles with a corona prior to their removal on collector plates or indoor surfaces and also emit ozone, which can react with terpenes to yield secondary organic aerosol, carbonyls, carboxylic acids, and free radicals. This study characterized the indoor air quality implications of operating an ion generator in a 27 m(3) residential room, with four different test room configurations. Two room configurations had carpet overlaying the original flooring of stained/sealed concrete, and for one configuration with and without carpet, a plug-in air freshener was used as a terpene source. Measurements included airborne sampling of particulate matter (0.015-20 μm), terpenes and C(1) -C(4) and C(6) -C(10) aldehydes, ozone concentrations, and air exchange rates. When the heating, ventilating, and air-conditioning system was not operating (room air exchange rate = ～0.5/h), the use of the ion generator in the presence of the air freshener led to a net increase in ultrafine particles (<0.1 μm). Also, increased concentrations of ozone were observed regardless of air freshener presence, as well as increases in formaldehyde and nonanal, albeit within measurement uncertainty in some cases. Thus, it may be prudent to limit ion generator use indoors until evidence of safety can be ascertained. PRACTICAL IMPLICATIONS: Portable ion generators are intended to clean the air of particles, but they may emit ozone as a byproduct of their operation, which has the potential to degrade indoor air quality. This study showed that under certain conditions in a residential room, the use of a portable ion generator can increase concentrations of ozone and, to a lesser degree, potentially aldehydes. Also, if operated in the presence of a plug-in air freshener that emits terpenes, its use can increase concentrations of secondary organic aerosol in the ultrafine size range.     

Surface chemistry reactions of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone and air on a glass and a vinyl tile

The surface-phase reaction products of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone (O(3)), air or nitrogen (N(2)) on both a glass and vinyl flooring tile were investigated using the recently published FLEC Automation and Control System (FACS). The FACS was used to deliver O(3) (100 ppb), air or N(2) to the surface at a specified flow rate (300 ml/min) and relative humidity (50%) after application of a 1.6%alpha-terpineol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine and N,O-bis(trimethysilyl)trifluoroacetamide. The positively identified reaction products were glyoxal, methylglyoxal and 4-oxopentanal. The proposed oxidation products based on previously published VOC/O(3) reaction mechanisms were: 4-methylcyclohex-3-en-1-one, 6-hydroxyhept-en-2-one, 3-(1-hydroxy-1-methylethyl)-6-methylcyclohex-2-en-1-one) and one surface-enhanced reaction product: 5-(1-hydroxy-1-methylethyl)-2-methylcyclohex-2-en-1-one. Though similar products were observed in gas-phase alpha-terpineol/O(3) reactions, the ratio of the reaction products were different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. PRACTICAL IMPLICATIONS: Volatile organic compounds (VOCs) can interact with indoor initiators [such as hydroxyl radicals (OH*), ozone and nitrate radicals (NO(3)*)] to form a number of oxygenated by-products in the gas-phase. However, when VOCs are applied to or are present on the surface, heterogeneous chemistry with indoor initiators can also occur. The surface can influence the reaction mechanism to produce new surface reaction products. The work, described here, shows the interaction of alpha-terpineol (major component of pine oil) with ozone and air on both glass and vinyl flooring. These results demonstrated emissions of oxygenated organic compounds as a result of reaction and that further investigations of this chemistry are required to accurately estimate indoor occupant exposures.     

Indoor boundary layer chemistry modeling

Ozone (O₃) chemistry is thought to dominate the oxidation of indoor surfaces. We consider the hypothesis that reactions taking place within indoor boundary layers result in greater than anticipated hydroxyl radical (OH) deposition rates. We develop models that account for boundary layer mass‐transfer phenomena, O₃‐terpene chemistry and OH formation, removal, and deposition; we solve these analytically and by applying numerical methods. For an O₃‐limonene system, we find that OH flux to a surface with an O₃ reaction probability of 10^?8 is 4.3 × 10^?5 molec/(cm² s) which is about 10 times greater than predicted by a traditional boundary layer theory. At very low air exchange rates the OH surface flux can be as much as 10% of that for O₃. This effect becomes less pronounced for more O₃‐reactive surfaces. Turbulence intensity does not strongly influence the OH concentration gradient except for surfaces with an O₃ reaction probability >10^?4. Although the O₃ flux dominates OH flux under most conditions, OH flux can be responsible for as much as 10% of total oxidant uptake to otherwise low‐reactivity surfaces. Further, OH chemistry differs from that for ozone; therefore, its deposition is important in understanding the chemical evolution of some indoor surfaces and surface films.     

Formation of strong airway irritants in terpene/ozone mixtures

The American Society for Testing and Materials (ASTM) mouse bioassay, which quantifies airway irritation from reduction in the respiratory rate, was used to find evidence for the formation of highly irritating substances in reactions of ozone with terpenes (common indoor volatile organic compounds (VOCs)). No-observed-effect-levels (NOELs) and concentration-effect relationships were established for ozone, (+)-alpha-pinene and R-(+)-limonene, isoprene, and some of their major reaction products. Reaction mixtures of excess terpene and ozone considerably below their NOEL concentrations resulted in significant upper airway irritation. The reduction of the respiratory rate was from 30% to about 50%, lowest for the alpha-pinene and highest for the isoprene mixture. Chemical analysis of reaction mixtures by conventional methods showed that readily identified stable products and residual reactants at the concentrations found could not account for the observed reductions of the respiratory rate, assuming additivity of the reaction products. The results suggest that, in addition to known irritants (formaldehyde, acrolein, methacrolein, methyl vinylketone), one or more strong airway irritant(s) of unknown structure(s) were formed. Future indoor air quality (IAQ) guidelines for unsaturated VOCs (e.g., terpenes) and their emission from building products may require the consideration of reactions with oxidants, like ozone. Similarly, effects of ozone-emitting equipment should be re-evaluated.     

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.     

Secondary VOC emissions from flooring material surfaces exposed to ozone or UV irradiation

Chemical reactions on the surface of building materials can lead to secondary emissions from these materials that influence indoor air quality. Many studies have been made on the physical processes that influence material emissions. However, there are only a few studies on secondary emissions resulting from exposure of building material surfaces to ozone or ultraviolet (UV) irradiation. Therefore, this study was aimed at elaborating on the emission of chemicals resulting from chemical reactions initiated by the exposure of the surface of flooring materials to ozone or UV irradiation. The laboratory tests were conducted to estimate gas-phase emissions from the flooring materials when they were exposed to ozone or various kinds of light irradiation (infrared, sunlight, UV-A and UV-B lamps). The infrared and sunlight lamps significantly increased the temperature of the test specimens and, in turn, increased the emission rate for various organic compounds. The flooring materials used in this study had been treated with UV-cured surface coatings during their manufacturing. As a result, when exposed to UV irradiation, chemical transformations occurred resulting in the emission of a number of secondary products, including formaldehyde, acetaldehyde, cyclohexanone and benzaldehyde. Ozone reacted with chemicals present in the flooring materials to increase the emission rates of formaldehyde and acetaldehyde. Hence, the exposure of ozone and UV irradiation increased the secondary emissions of formaldehyde, even though the low formaldehyde emission type of flooring material was employed.     

Outdoor ozone and building-related symptoms in the BASE study

Reactions between ozone and indoor contaminants may influence human health and indoor air quality. The U.S. EPA Building Assessment Survey and Evaluation (BASE) study data were analyzed for associations between ambient ozone concentrations and building-related symptom (BRS) prevalence. Multiple logistic regression (MLR) models, adjusted for personal, workplace, and environmental variables, revealed positive relationships (P < 0.05) between ambient ozone concentrations and upper respiratory (UR), dry eyes, neurological and headache BRS (odds ratios ranged from 1.03 to 1.04 per 10 mug/m(3) increase in ambient ozone concentrations). Other BRS had marginally significant relationships with ambient ozone (P < 0.10). A linear dose-response in UR symptoms was observed with increasing ambient ozone (P = 0.03); most other symptoms showed similar but not statistically significant trends. Ambient ozone correlated with indoor concentrations of some aldehydes, a pattern suggesting the occurrence of indoor ozone chemistry. Coupled with the MLR ambient ozone-BRS analysis, this correlation is consistent with the hypothesis that ozone-initiated indoor reactions play an important role in indoor air quality and building occupant health. Replication with increased statistical power and with longitudinal data is needed. If the observed associations are confirmed as causal, ventilation system ozone removal technologies could reduce UR BRS prevalence when higher ambient ozone levels are present. PRACTICAL IMPLICATIONS: This paper provides strong statistical evidence that supports (but does not prove) the hypothesis that ozone entrained into buildings from the outdoor air is involved in increasing the frequency that occupants experience and a range of upper and lower respiratory, mucosal and neurological symptoms by as much as a factor of 2 when ambient ozone levels increase from those found in low-ozone regions to those typical of high-ozone regions. Although replication is needed, the implication is that reducing the amount of ozone entrained into building ventilation systems, either by ambient pollution reduction or engineered gas-phase filtration, may substantially reduce the prevalence of these symptoms experienced by occupants.     

Chemistry in indoor environments: 20 years of research

In the two decades since the first issue of Indoor Air, there have been over 250 peer-reviewed publications addressing chemical reactions among indoor pollutants. The present review has assembled and categorized these publications. It begins with a brief account of the state of our knowledge in 1991 regarding 'indoor chemistry', much of which came from corrosion and art conservation studies. It then outlines what we have learned in the period between 1991 and 2010 in the context of the major reference categories: gas-phase chemistry, surface chemistry, health effects and reviews/workshops. The indoor reactions that have received the greatest attention are those involving ozone-with terpenoids in the gas-phase as well as with the surfaces of common materials, furnishings, and the occupants themselves. It has become clear that surface reactions often have a larger impact on indoor settings than do gas-phase processes. This review concludes with a subjective list of major research needs going forward, including more information on the decomposition of common indoor pollutants, better understanding of how sorbed water influences surface reactions, and further identification of short-lived products of indoor chemistry. Arguably, the greatest need is for increased knowledge regarding the impact that indoor chemistry has on the health and comfort of building occupants. PRACTICAL IMPLICATIONS: Indoor chemistry changes the type and concentration of chemicals present in indoor environments. In the past, products of indoor chemistry were often overlooked, reflecting a focus on stable, relatively non-polar organic compounds coupled with the use of sampling and analytical methods that were unable to 'see' many of the products of such chemistry. Today, researchers who study indoor environments are more aware of the potential for chemistry to occur. Awareness is valuable, because it leads to the use of sampling methods and analytical tools that can detect changes in indoor environments resulting from chemical processes. This, in turn, leads to a more complete understanding of occupants' chemical exposures, potential links between these exposures and adverse health effects and, finally, steps that might be taken to mitigate these adverse effects.     

Spatial distributions of ozonolysis products from human surfaces in ventilated rooms

Ozone has adverse effects on human health. Skin oil on the human surface acts as an ozone sink indoors, producing oxidation products that can cause skin and respiratory irritations. Concentrations of ozone and oxidation products near human surfaces, including the breathing zone, can be modulated by indoor ventilation modes and human surface conditions. The objective of this study is to examine concentrations and spatial heterogeneity of ozone and ozonolysis products under representative ranges of indoor ventilation, clothing, and breathing conditions. Using computational fluid dynamics (CFD) simulation in conjunction with a chemical kinetic model, details of ozone reactions with the human surface and subsequent chemical reactions are examined. The results show that primary ozonolysis products are concentrated near the soiled clothing, while the secondary products are relatively well distributed throughout the room. Increasing indoor air mixing enhances the ozone deposition to the human surface, thereby resulting in higher emission rates of oxidation products in the room. Soiled clothing consumes more ozone than clean clothing and accordingly produces ~ 65% more primary products and ~15% more secondary products. The results also reveal that unsaturated hydrocarbons from the human breath, such as isoprene, contribute to only ~0.5% of ozone removal compared to ozone deposition to the human surface.     

Impact of surface ozone interactions on indoor air chemistry: A modeling study

An INdoor air Detailed Chemical Model was developed to investigate the impact of ozone reactions with indoor surfaces (including occupants), on indoor air chemistry in simulated apartments subject to ambient air pollution. The results are consistent with experimental studies showing that approximately 80% of ozone indoors is lost through deposition to surfaces. The human body removes ozone most effectively from indoor air per square meter of surface, but the most significant surfaces for C₆‐C₁₀ aldehyde formation are soft furniture and painted walls owing to their large internal surfaces. Mixing ratios of between 8 and 11 ppb of C₆‐C₁₀ aldehydes are predicted to form in apartments in various locations in summer, the highest values are when ozone concentrations are enhanced outdoors. The most important aldehyde formed indoors is predicted to be nonanal (5‐7 ppb), driven by oxidation‐derived emissions from painted walls. In addition, ozone‐derived emissions from human skin were estimated for a small bedroom at nighttime with concentrations of nonanal, decanal, and 4‐oxopentanal predicted to be 0.5, 0.7, and 0.7 ppb, respectively. A detailed chemical analysis shows that ozone‐derived surface aldehyde emissions from materials and people change chemical processing indoors, through enhanced formation of nitrated organic compounds and decreased levels of oxidants.     

Ozone in Residential Air: Concentrations,I/O Ratios,Indoor Chemistry,and Exposures

Ozone concentrations were measured in indoor and outdoor residential air during the summer of 1992. Six homes located in a New Jersey suburban area were chosen for analysis, and each home was monitored for 6 days under different ventilation and indoor combustion conditions. The 5-hour average ozone concentration outdoors over the monitoring period was 95 ± 36 ppbv. One third of the days exceeded the National Ambient Air Quality Standard (NAAQS), one-hour maximum concentration of 120 ppb. The mean indoor to outdoor (I/O) ratios of ozone concentration ranged from 0.22 ± 0.09 to 0.62 ± 0.11, depending upon ventilation rate and indoor gas combustion. The presence of indoor gas combustion can significantly decrease the I/O ratio. Because of the great amount of time that people spend indoors, the indoor residential exposures were estimated to account for 57% of the total residential exposures. One type of the possible gas-phase reactions for indoor ozone, the reaction of ozone with a volatile organic compound containing unsaturated carbon-carbon bonds, is discussed with some supporting evidence provided in the study.     

The eye irritation and odor potencies of four terpenes which are major constituents of the emissions of VOCs from Nordic soft woods

Eye goggles were used to estimate human thresholds for sensory eye irritation from four monoterpenes: (+)3-carene, (-)limonene and (+)alpha-pinene and (rac)alpha-terpineol all known as air pollutants emitted from wood. Only a ranking of the irritation thresholds relative to that of n-butanol is given. The measurements showed that the thresholds for eye irritation of the terpenes ranged from subthreshold to below 1,250 mg/m3. It appears that the irritation of 3-carene and limonene in contrast to the expectations was of the same size as or less than that of n-butanol. Too few subjects reported eye-irritation for alpha-pinene and alpha-terpineol to allow estimates of thresholds of these compounds which therefore have much less irritative potency than n-butanol, 3-carene, and limonene. The measurements of one terpene alcohol do not support the hypothesis that monoterpene alcohols, would have lower eye irritation threshold than monoterpene hydrocarbons. The sequence from strongest odorant to weakest was alpha-terpineol, 3-carene, n-butanol, limonene and alpha-pinene. In conclusion, the tested terpenes can probably be ruled out as cause of acute eye irritation indoors. The measured odor thresholds did not deviate from the few values reported in the literature.     

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.     

Ultrafine particle emission from floor cleaning products

The new particle formation due to the use of cleaning products containing volatile organic compounds (VOCs) in indoor environments is well documented in the scientific literature. Indeed, the physical-chemical process occurring in particle nucleation due to VOC-ozone reactions was deepened as well as the effect of the main influencing parameters (ie, temperature, ozone). Nonetheless, proper quantification of the emission under actual meteo-climatic conditions and ozone concentrations is not available. To this end, in the present paper the emission factors of newly generated ultrafine particles due to the use of different floor cleaning products under actual temperature and relative humidity conditions and ozone concentrations typical of the summer periods were evaluated. Tests in a chamber and in an actual indoor environment were performed measuring continuously particle number concentrations and size distributions during cleaning activities. The tests revealed that a significant particle emission in the nucleation mode was present for half of the products under investigation with emission factors up to 1.1 × 10¹¹ part./m² (8.8 × 10¹⁰ part./mL_product), then leading to an overall particle emission comparable to other well-known indoor sources when cleaning wide surfaces.     

The influence of ammonia and carbon dioxide on the sorption of a basic organic pollutant to a mineral surface

Indoor surfaces have a sorptive capacity for organic pollutants which may be significantly influenced by other gases and the pH of the surface. In this research, we examine the influence of a common indoor gaseous acid, CO2, and base, NH3, on the adsorption of a volatile organic base, trimethylamine (TMA), to a mineral surface, zirconium silicate beads. Varying ammonia and CO2 within concentration ranges of indoor relevance substantially influences the sorptive capacity of this mineral surface. Increasing the CO2 mixing ratio to 1000 p.p.m. enhances surface capacity of TMA by 40-50%; increasing the NH3 mixing ratio to 10 p.p.m. decreases the TMA surface capacity by approximately 5-80% depending on relative humidity. The phenomena of dissolution of TMA into bulk surface water and acid-base chemistry in the surface water do not adequately describe equilibrium adsorption on this surface. Instead, adsorption to the dry solid or to adsorbed water layers appears to dominate. Reduction in the equilibrium partition coefficient, ke, in the presence of NH3 is due to a competition between TMA and ammonia molecules for adsorption sites. Site competition appears to follow the Langmuir competitive model and most ke values range from 0.003-0.045 m. PRACTICAL IMPLICATIONS: Sorptive interactions with indoor surfaces strongly influence indoor exposure to pollutants. For basic or acidic compounds, these interactions are themselves influenced by surface pH and competition with other acidic or basic gases such as CO2 and NH3. We show that CO2 tends to cause mineral surfaces to store more amines but NH3 tends to decrease this surface capacity. Given the typical range of indoor CO2 and NH3 concentrations, the indoor sorbtive capacity of amines on mineral surfaces may vary by greater than an order of magnitude.     

Indoor ozone/human chemistry and ventilation strategies

This study aimed to better understand and quantify the influence of ventilation strategies on occupant‐related indoor air chemistry. The oxidation of human skin oil constituents was studied in a continuously ventilated climate chamber at two air exchange rates (1 h^?1 and 3 h^?1) and two initial ozone mixing ratios (30 and 60 ppb). Additional measurements were performed to investigate the effect of intermittent ventilation (“off” followed by “on”). Soiled t‐shirts were used to simulate the presence of occupants. A time‐of‐flight‐chemical ionization mass spectrometer (ToF‐CIMS) in positive mode using protonated water clusters was used to measure the oxygenated reaction products geranyl acetone, 6‐methyl‐5‐hepten‐2‐one (6‐MHO) and 4‐oxopentanal (4‐OPA). The measurement data were used in a series of mass balance models accounting for formation and removal processes. Reactions of ozone with squalene occurring on the surface of the t‐shirts are mass transport limited; ventilation rate has only a small effect on this surface chemistry. Ozone‐squalene reactions on the t‐shirts produced gas‐phase geranyl acetone, which was subsequently removed almost equally by ventilation and further reaction with ozone. About 70% of gas‐phase 6‐MHO was produced in surface reactions on the t‐shirts, the remainder in secondary gas‐phase reactions of ozone with geranyl acetone. 6‐MHO was primarily removed by ventilation, while further reaction with ozone was responsible for about a third of its removal. 4‐OPA was formed primarily on the surfaces of the shirts (~60%); gas‐phase reactions of ozone with geranyl acetone and 6‐MHO accounted for ~30% and ~10%, respectively. 4‐OPA was removed entirely by ventilation. The results from the intermittent ventilation scenarios showed delayed formation of the reaction products and lower product concentrations compared to continuous ventilation.     

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.