Ozone Initiated Secondary Emissions of Aldehydes from Indoor Surfaces

Paper # 1232 Hong Wang, Meredith Springs, Glenn Morrison University of Missouri-Rolla, 1870 Miner Circle, Rolla, MO 65409

ABSTRACT
Secondary emissions of oxidized organic compounds, primarily aldehydes, from building surfaces in the presence of ozone may contribute significantly to indoor air pollution. Ozone-induced formation of aldehydes was studied to determine how daily use consumer products contribute to secondary emissions. A field ready method was developed to quantify secondary emission rates on existing surfaces. Four different products, canola cooking oil, a spray cooking oil, bath soap, and a liquid detergent, were evaluated after being coated on a laminated countertop. Upon exposure to 100 ppb O3, nonanal and hexanal were emitted at rates similar to secondary emission rates from carpet. Total aldehyde emission rates from canola oil, soap, and spray cooking oil were respectively 180, 110, 125 g m-2 h-1. The liquid detergent released small amounts of hexanal, octanal, and nonanal. The aldehyde emission pattern from these products roughly correspond to the anticipated relative aldehyde emission rates due to the proportion of unsaturated fatty acids in vegetable oils and animal fats. If a substantial area of indoor surfaces are coated with these products, secondary emission rates of aldehydes (especially nonanal) may result in concentrations approaching or exceeding odor thresholds.

INTRODUCTION
The emissions of organic compounds in buildings are of great concern due to their potential to cause sick-building syndrome, cancer, irritation, and unpleasant odors. Past research has focused on primary emissions of organic compounds; however, researchers are beginning to also look at secondary emissions. Secondary emissions of volatile organic compounds (VOCs) are defined as emissions resulting from transformations taking place indoors, significantly increasing the concentrations of odorous and irritating compounds such as aldehydes. This paper discusses our research that evaluates the possibility that daily-use consumer products, such as soaps and cooking oils, can react with ozone on surfaces to produce secondary emissions (aldehydes).

Weschler et al.1 was the first to show that ozone reacted with carpet to form formaldehyde, acetaldehyde, and aldehydes containing between five and ten carbons. They proposed that the source of the homologous series of C5-C10 aldehydes was the reaction between ozone and condensed-phase material associated with carpets. Other

indoor sources, such as paint, were also studied, and results showed organic acids and carbonyl groups (aldehydes and ketones) were formed as a result of latex paint exposure to ozone2. Morrison et al.3,4 showed secondary aldehydes, especially nonanal, were the result of reactive chemistry between ozone and carpet surfaces. They demonstrated particular aldehydes may emit at rates high enough to exceed the odor threshold for long periods of time. They found evidence that the carpet was coated with unsaturated fatty acids, or nonvolatile polymers with some degree of unsaturation.

Morrison et al.4 anticipated these surface precursors compounds would eventually become depleted as ozone oxidized the limited number of unsaturated bonds in the coating.To our knowledge, researchers have not evaluated the potential for daily use consumer products to produce aldehydes via reactions with ozone. Product such as soaps and oils are composed of unsaturated fatty acids or esters. During normal consumer use of these products, indoor surfaces may become covered with chemically reactive species that will emit aldehydes and carboxylic acids in the presence of ozone. For example, cooking oils evaporate somewhat during cooking and condense on nearby surfaces. Soaps precipitate in hard water and may remain on surfaces even after rinsing. Consumer products can generate aldehydes on surfaces that do not otherwise react with ozone (e.g. laminated kitchen countertops) or they may regenerate the potential for secondary emissions from depleted surfaces (e.g. carpet). Since we are most interested in identifying how consumer use of products can enhance the ability of a surface to chemically produce oxidized volatile products, we recognized the importance of being able to evaluate secondary emission rates on real, in-use, indoor surfaces. The field and laboratory emission cell (FLEC) has been used widely for measuring the primary emission rates of VOCs from existing surfaces. However, it was unclear if this device was suitable for measuring secondary emission rates which incorporate deposition and emission in one chamber. To our knowledge, no field ready method has been developed to measure secondary emission rates from existing indoor surfaces. Therefore, the objectives of this paper are (1) to develop methods to measure secondary emission rates of aldehydes in residential field experiments; and (2) to evaluate the secondary emission rates from consumer products that may coat a kitchen countertop during normal use.

MATERIALS AND METHODS Consumer Products

Four commonly used products were tested in this study: cooking canola oil, spray cooking oil (Pam), bath soap (Ivory), and a liquid dish detergent (Palmolive), These products contain long, unsaturated, fatty acids from either animals or plant sources. In Table 1 are shown the anticipated fatty acid content of canola oil and animal fats.

Coating Methods
A laminated countertop was used as the test surface and coated with various consumer products. First, the countertop was cleaned with methanol and rinsed with distilled water. Then, the countertop was coated with the products in the same manner as they are used in homes. The coating methods are as follows. (1) Canola oil. Before being coated, half of the countertop was covered with aluminum foil and half remained uncovered. This technique represented an unexposed and exposed surface, respectively. The countertop was placed near a stove where 5g of canola oil was cooked with fresh tomatoes and eggs. In the process of cooking, vaporized oil deposited on the exposed side of the countertop. No visible droplets of oil or obvious splatters were observed on the panel. (2) Soap. A bar of bath soap was wetted and rubbed uniformly on the counter top. The soap lather was rinsed using tap water. (3) Spray cooking oil. The cooking oil was sprayed on a piece of paper held perpendicular to the countertop surface (as a consumer might spray a pan before cooking), allowing excess spray droplets to settle naturally on the countertop surface. (4) Detergent. The detergent was used to clean the countertop. For one experiment, the detergent cleaned top was rinsed with tap water later. For the other experiment, the top was not rinsed with water after cleaning.

Table 1. Chemical composition of oil and soap

Fat type Canola oil (rapeseed oil) (cooking oil and spray cooking oil)

Animal fat or tallow

Fatty acid composition 5 Palmitic 2.3% Stearic 2.3% Acachidic 1.1% Behenic 1.2% Lignoceric 0.7% Hexadecenoic 1.6% Oleic 15.0% Eicosenoic 6.2% Erucic 46.5% Linoleic 13.8% Docosadienoic 1.0% Linolenic 8.5% Lauric 0.2%

Notes Average fatty acid percentages for rapeseeds from various countries.

Average fatty acid

(soap and detergent)

Myristic 4.4% Palmitic 29.8% Stearic 22.5% Arachidic 1.0% Tetradecenoic 0.4% Hexadecenoic 1.7% Oleic 39.8% Octadecadienoic 1.8% C20-C22 unsaturated 0.4%

percentages for beef from various countries.

Secondary Emission Rate Experiments

Secondary emissions of aldehydes formed by reactions between consumer products and ozone were measured using the apparatus shown in Figure 1. The system consisted of an ozone generator, humidifier, field emission chamber, sampling system, and an UV photometric ozone analyzer. The 4.25-L Teflon-coated field emission chamber is open on the bottom so that it can be positioned on the surface, isolate a defined area of the surface, collect emissions and deliver reactants (e.g. ozone) to that surface. Compressed air was introduced into the system and split between three streams. The air stream was passed through a humidifier (two gas sparging bottles, filled with distilled water, in series) before being mixed with an additional stream to produce air with a relative humidity of 505%. The third air stream passed through an ozone generator and then mixed with the humidified air. The chamber was continuously ventilated at 2.00.01 L min-1 of either humidified air or humidified air containing ozone. A three-way valve located in front of the chamber was used to measure ozone concentrations at the chamber inlet. Stainless steel sampling tubes packed with Tenax-TA tubes were attached to the chamber exhaust to collect samples. A Tenax-TA tube sampling airflow rate of 0.1 L min-1 was controlled by the use of a sampling pump and flow splitter. The sampling air flow rate was continuously monitored by a mass flow meter. Sample volume was 2.0 L. VOC emissions were measured before and after the system was exposed to ozone. Inlet and outlet concentration measurements were used to determine the ozone deposition on the surface.

Prior to the experiment, the laminated countertop was either cleaned using soap/ detergent or exposed to cooking oil (see enumerated list). Then the test chamber was placed on top of the panel, with a narrow ring of foam ensuring a tight seal between the chamber and surface. Ozone-free humidified air was introduced into the system for one hour. Two samples, representing emissions from unexposed products, were collected at the exhaust point. The system was then exposed to an ozone concentration of approximately 100 ppb for one hour with subsequent samples collected. A final sample was obtained at the chamber inlet to represent a system blank.

System Leak Test

Surface emission chambers that are intended to seal onto the surface itself (instead of completely enclosing a surface sample) may leak around the point of contact between the chamber and the surface, especially if the surface is not smooth. The apparatus shown in Figure 2 was designed to test the total leakage rate for the chamber. The leak test conditions were the same as those for the secondary emission rate measurements, except that a sulfurhexafluoride monitor (INOVA 1302) was positioned at the sampling stream. Sulfur hexafluoride was used as tracer gas, and a known mass was injected into the inlet point A, as shown in Figure 2. Assuming the system acts as a completely-mixed flow reactor model, the gas exchange rate was determined from the rate of decrease of the concentration of sulfurhexafluoride during a 0.5 h period. The percent leakage was determined by comparing the % difference between the estimated and measured gas exchange rates. Figure 1. Experimental apparatus for measuring ozone-induced secondary emission rates from in-use surfaces.

humidifier

4.25L teflon coated chamber

counter-top mass-flow controller ozone generator UV Absorption ozone analyzer tenax tube mass-flow meter mass-flow flow sampling meter splitter pump

Air

vacuum pump

Figure 2. System leak test. Sulfurhexafluoride was injected into the inlet branch at position A and the concentration decay was measured at the exhaust to determine the actual gas exchange rate.

hu m idifier

4.2 5L teflon co ated ch am ber

cou nter-to p m ass-flo w co ntro ller o zone g enerator m ulti-g as m o nitor m ass-flow m eter

Air

vacuu m pu m p

Target Analyte Measurement

Analytes collected on Tenax-TA sample tubes were analyzed using a thermal desorber/gas chromatograph/ flame-ionization detector (TD/GC/FID) system with an autosampler. Tubes were desorbed at 140C for 10 minutes. The TD cold-trap was then desorbed at 150C before the gas was carried into the GC for analysis. The GC inlet pressure was 14.7 psi with a total gas flow rate of 7.3 mL min-1, operated in split-less and constant pressure modes. The oven temperature was initially set at 50C and held there before increasing at a rate of 30C min-1 up to a maximum temperature of 250C. The FID was set at 250C with gas flows as follows: hydrogen, 40 mL min -1; compressed air, 450 mL min-1, and nitrogen, 45 mL min-1. Analytes diluted in methanol were used as standards for system calibration of aldehydes. By a double dilution method, a methanol solution composed of 3 mg L-1 of each aldehyde was created. For example, 505 L samples of each pure aldehyde liquid were injected into a 25 mL volumetric flask containing 25 mL of acetone-free methanol. The sample was sonicated for ten seconds to ensure complete mixing. A 505 L sample of this

mixture was injected into a second volumetric flask containing 25 mL of acetone-free methanol and further sonicated. From this final dilution, samples representing approximately 50 and 100 ng (162 and 324 L) of the aldehyde solution were injected onto the inlet packing of a clean Tenax TA tube and analyzed using the same TD/GC/FID method described above for the air samples. Using the data obtained from the GC, standard calibration curves were generated based on plots showing the peak area versus the mass. Calibrations curves for pentanal, hexanal, heptanal, octanal, nonanal, decanal, 2-nonenal, and 2,4-nonadienal were generated.

RESULTS AND DISCUSSIONS Methods Development

The method used in this study was developed to test for secondary emissions from in-use surfaces in residential field experiments. We found that the method consistently provided reproducible secondary emission rate measurements. For example, the average emission rates standard deviation for duplicate measurements was about 13% for canola oil, soap, and Pam. Leak tests are vital to ensuring reliability of secondary emission rate measurements. For these experiments, a leakage fraction of <0.1 was considered acceptable. In the future, positive and negative control experiments will be developed to improve our confidence in the method results.

Secondary Emissions
Several consumer products tested in this research generated secondary carbonyl emissions in the presence of ozone. Results of these experiments are reported in terms of the analyte mass emission rate per exposed surface area (g m-2 h-1). In Figure 3 are shown the ozone induced secondary aldehyde emission rates. Uncertainty bars represent error propogation of the standard error of calibrations and replicate experiments for each product. Secondary mass emission rates were obtained by subtracting the emission rate of unexposed products from the emission rate of exposed products. While most of the target aldehydes were observed to be emitted from each consumer product, nonanal was the most prominent secondary aldehyde. Nonanal was emitted in significant amounts from the cooking vapor deposited canola oil, soap, and spray canola oil. Total secondary emission rates of aldehydes, of the order of 150 g m-2 h-1, are comparable to or higher than ozone-induced secondary emission rates from carpet4. The secondary emission rates from the detergent, with and without a tap water rinse, were small, but the relative emission rates of nonanal, hexanal and octanal were remarkably similar to one another. This suggests that a film of detergent remains on the surface even after rinsing. While detergents should rinse somewhat thoroughly, rinsing soaps with hard water is likely to leave a substantial film of unsaturated soap precipitate that can act as a source of oxidized products. When the countertop was exposed to cooking vapor deposited canola oil, nonanal was the primary compound produced. A small amount of hexanal was also emitted. Nonanal and hexanal were also observed for the spray canola oil; however, the spray released more

hexanal than the cooking vapor deposited canola oil. As listed Table 1, canola oil consists predominantly of 18-carbon, unsaturated, fatty chains such as oleic acid, linoleic acid, and linolenic acid and eurcic acid, a 22-carbon unsaturated fatty acid. Ozone will attack the double-bonds in these esters, forming aldehydes and carboxylic acids at the point of attack. For example, nonanal and 3-nonenal will be formed when ozone attacks the ninth carbon of the esters of erucic (nonanal), oleic (nonanal), and linoleic acids (3-nonenal). Similarly, 3, 6-nonadienal is the product of the ozonation of the double-bond located at the ninth carbon of linolenic acid. Hexanal, 3-hexenal, and propanal are also released from the reaction of canola oil and ozone. Canola oil may have been transformed by cooking or by processing so that oleic acid dominates. As a result, aldehydes released from canola oil were not consistent with reported proportions of oleic and linoleic acid. However, the spray canola oil appeared more consistent than the vapor deposited from cooking canola oil. The emission patterns of secondary aldehydes (i.e. relative emission rates), from soap were similar to those observed during carpet experiments 4. Soaps are made by rendering animal tallow with a strong alkali to produce saturated fatty acids, such as stearic acid, as well as unsaturated fatty acids, such as oleic acid. The secondary emissions of aldehydes from soap were expected to be similar to those from oils given the relative composition of tallow; however, a different pattern was observed. Pattern variations may have been caused by a shift in the unsaturated bond of the esters during processing with a strong base. For example, shifting the double-bond one position away from the acid functionality would result in octanal upon oxidation. Two shifts results in heptanal and so forth. The declining relative emission rates from nonanal down to pentanal suggests this may be the case. However, we did not observe decanal, the secondary product generated if the double-bond shifted one position towards the carboxylic acid functional group. Small relative amounts of secondary aldehydes were observed for the detergent. This suggested the chemical constituents of detergent do not have many unsaturated double bonds. Small amounts of oleic acid may have been present during the sulfonation process, resulting in small amounts of sulfonated, unsaturated precursors being produced. Figure 3 shows that hexanal, octanal, and nonanal were consistently emitted at low secondary emission rate from the detergent. For the clean panel, a negative emission rate of pentanal was observed. We believe this was due to a contaminated sampling tube which produced an artificially high baseline. The emissions of other aldehydes, such as heptanal, nonanal and decanal were probably caused by a modest primary emission from panel. Figure 3. Secondary aldehyde emission rates for each consumer product.

Aldehyde Formation Factors

The ozone-induced aldehyde formation factor is an indicator of secondary carbonyl emissions based on the assumption that secondary-product emission rates are proportional to ozone deposition rates. The factor is defined as the ratio of the ozoneinduced molar emission rate of carbonyl species to the molar loss rate of ozone to that surface. Shown in Figure 4 are emission formation factors for target aldehydes composed of five to ten carbons. Typically, the nonanal formation factor for oil and soap is ~0.2, indicating 20% of the uptake ozone produced nonanal via ozone-product reactions. The total of all detected aldehydes should theoretically equal 0.5 since the ozone-product reaction will produce aldehydes 50% of the time and carboxylic acids the other 50% of the time. The summed formation for all target aldehydes ranged between 0.2 and 0.4, less than the expected 0.5. This may be due to the fact that we were unable to positively identify or quantify some aldehydes (such as 3-nonenal), or any short-chain aldehydes. Negative formation factors and large uncertainties observed for one detergent experiment was due to very low total ozone uptake for that experiment. Figure 4: Ozone-induced aldehydes formation factor of each consumer product. The category detergent1 represents the countertop that has been cleaned with detergent but rinsed with tap water. The category detergent2 represents detergent that was not rinsed off.

-2

h )

-1

The influence on indoor air quality of secondary aldehyde emissions from consumer products
Using our observed formation factors, we can estimate the indoor concentrations of target aldehydes that are emitted as a result of ozone oxidation of unsaturated fatty acids. We consider nonanal emitted from the laminated countertop (exposed to cooking vapor deposited canola oil) as an example. The emission rate of an aldehyde can be estimated by combining the aldehyde formation factor with the anticipated ozone flux to the countertop surface. The indoor ozone concentration is estimated based on a steady-state material balance model6 of a well-mixed residence. Given typical indoor conditions: (a) outdoor ozone concentration, 25ppb7; (b) average deposition velocity, 1.4m h-1 8; (c) air exchange rate, 0.5h-1 9; (d) estimated area-to-volume ratio, 3m-1,the calculated timeaveraged indoor ozone concentration is 2.7ppb. A carpet-specific deposition velocity of 1m h-1 for ozone4 is combined with indoor ozone concentration to estimate the ozone flux. The secondary emission rate of the aldehyde is obtained by multiplying ozone flux by our observed nonanal formation fraction, 0.2. We assume that nonanal was not present in outdoor air and was produced only by the canola oil-ozone reaction. For nonanal, the estimated emission rate was 4.5 g m-2 h-1. Assuming that the countertop exposed area to kitchen volume ratio was 0.1 m-1, the resulting indoor nonanal concentration was 0.9 g m-3. This concentration is lower than the nonanal odor threshold of 13 g m-3. Since oils present on the floor, walls, and ceiling from cooking were not take into account, this may be a substantial underestimate of the impact of these ozone induced emissions. Since other products such as 3-nonenal and 3,6-nonadienal (not quantified in this research) have much lower odor thresholds, consumer usage of these products may indeed degrade indoor air quality due to ozone reactions.

CONCLUSIONS

Our experimental results demonstrate that in-use consumer products react with ozone to produce aldehydes. The secondary emission rates and formation factors are comparable to those observed for carpet, which were estimated to significantly degrade indoor air quality4. While fresh carpet may still be the major source of these aldehydes indoors, time softens the impact as ozone eventually depletes the precursor unsaturations on the surface. However, daily use of cooking oils, soaps and other products may regenerate these surfaces, continuously supplying precursor unsaturated fatty acids. Since many personal hygiene products also contain unsaturated fatty acids (we note that the major ingredient in a popular facial cleanser in the United States is C14-C16 olefin sulfonate), these reactions are also likely to take place on the skin immediately adjacent to the breathing zone, further degrading the personal cloud. Even natural skin oils themselves could contribute to secondary emissions of oxidized volatile organic compounds. It is presently unclear the extent to which consumer products contribute to the secondary emission of aldehydes in indoor air. One objective of our laboratory research on consumer product reactions with ozone is to simulate residential field studies. Our next step is to take a validated field emission chamber to residences to evaluate in-use surfaces for secondary emission rates. In addition, we hope to develop methods to measure other products such as carboxylic acids which may have a greater impact on odor and or irritation potential of indoor air. ACKNOWLEDGEMENTS This research is funded by the National Science Foundation through a CAREER award fellowship. We thank Maneerat Ongwandee for her assistance with the experiments.

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Nazaroff, W.W.; Gadgil, A.J.; Weschler, C.J. Nagda, N.L.; Ed.; STP 1205, American Society for Testing and Material: Philadelphia, PA, 1993; pp 81-104. 9. Murray, D.M.; Burmaster, D.E. Risk Anal. 1995, 15, 459.