Reactive Aging of Films of Secondary Organic Material Studied by

Dec 13, 2012 - 4, Roosevelt Road, Taipei, 10617 Taiwan ... Barbara Nozière , Markus Kalberer , Magda Claeys , James Allan , Barbara D'Anna , Stefano ...
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Reactive Aging of Films of Secondary Organic Material Studied by Infrared Spectroscopy Hui-Ming Hung,*,† Yu-Quan Chen,† and Scot T. Martin‡ †

Department of Atmospheric Sciences, National Taiwan University No. 1, Sec. 4, Roosevelt Road, Taipei, 10617 Taiwan School of Engineering and Applied Science & Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts 02138, United States



S Supporting Information *

ABSTRACT: The reactive aging of films of secondary organic material (SOM) to ozone, irradiation, and water was studied by attenuated total reflectance infrared spectroscopy (ATRIR). The films were prepared by deposition onto the ATR elements of particles produced by reaction of isoprene with hydroxyl radicals and of α-pinene with ozone in the Harvard Environmental Chamber (HEC). The infrared spectra showed that the isoprene-derived film had strong hydroxyl absorptions whereas the α-pinene-derived film had strong carbonyl absorptions. The organic films were exposed to dry and humid flows of ozone, as well as to ultraviolet irradiation, to mimic reactive aging processes that can occur in the troposphere. Both the isoprene- and α-pinene-derived films were nonreactive with respect to ozone exposure, for both dry and humid conditions, indicating that the secondary organic material consisted mostly of saturated organic species. Both films, however, were susceptible to aging by ultraviolet radiation possibly due to the presence of organic hydroperoxides, and all functional groups other than carbonyls decreased upon irradiation. In regard to hygroscopicity, as a benchmark the ratio xW_CO for oxalic acid of the intensity of the water-bending peak to that of carbonyl absorption (arising from carboxylic acids) was recorded from 20% to 80% relative humidity (RH). This quantity was then also measured for the isoprene- and α-pinene-derived organic films. The result of (xW_CO)isoprene > (xW_CO)benchmark across the range of studied RH values shows that species other than carboxylic acids contributed significantly to the hygroscopicity of the isoprene-derived film. The spectra were consistent with alcohols and hydroperoxides as the hygroscopic components. By comparison, the result of (xW_CO)pinene ≈ (xW_CO)benchmark indicates a dominance of carboxylic acids with respect to the hygroscopicity of this film.

1. INTRODUCTION Aerosol particles have an important role in climate due to their efficacy in absorbing and scattering solar radiation and their ability to act as cloud condensation nuclei, further affecting the cloud albedo.1−7 How aerosol particles affect radiation is dependent on their physical properties, which in turn can depend on chemical composition. In the case that particle composition is significantly hygroscopic, the particles take up water as relative humidity (RH) increases, growing into larger particles that scatter more radiation. The larger surface area, coupled to the moist surface properties, also increases rates of gas−particle reactions in the atmosphere.8−12 In the atmosphere, aerosol particles are emitted both directly from the surface of the Earth, such as dust and sea salt particles, and indirectly by oxidation reactions of volatile species that in come cases can produce less-volatile products. This indirect pathway can include nucleation and condensation processes, leading to the production of secondary organic aerosol, with precursors contributed via both anthropogenic and natural sources.7,13,14 The presence of organic species in the particle phase tends to complicate the physical properties of the pre© 2012 American Chemical Society

existing aerosol particles due to changes in chemistry and surface tension.3,15 The physical properties of organic species, such as the volatility and solubility, depend on the carbon chain length and also the functional groups in the molecules. However, because of the complexity of organic species, the identification of particle composition is still under investigation using different detection methods. To quantify the hygroscopicity of aerosol particles, several different complementary techniques are described in the literature to monitor how the particles grow as RH varies, e.g., electrodynamic balance (EDB) measures the particle mass variation as RH changes,16−19 tandem differential mobility analyzer (TDMA) monitors the diameter variation of selected particles as a function of RH,20−25 optical microscopy monitors the morphological variation,18,26−28 and aerosol flow tube with IR detection (AFT-IR) detects the water absorption peaks for the suspended particles.29−34 In this study, we used the Received: March 14, 2012 Revised: November 14, 2012 Published: December 13, 2012 108

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technique of attenuated total reflectance with infrared detection (ATR-IR) to characterize the functional groups of particles deposited as films of secondary organic material (SOM) on an inert ATR substrate, with a focus on hygroscopicity. Infrared spectroscopy provides information on the types and the relative concentrations of chemical functional groups that are present within organic material.35−38 The effects of ozone, ultraviolet irradiation, and water were investigated.

PFA Teflon bag and was operated as a steady-state continuousflow mixed reactor with a resident time of 3.5 h. More detailed descriptions have been provided previously.43−48 The particles in the outflow from the HEC were characterized by a scanning mobility particle sizer (SMPS, TSI 3936) to obtain the numberdiameter distribution and by a high-resolution time-of-flight Aerodyne aerosol mass spectrometer (HR-ToF-AMS)43,46,49 to assay organic particle mass concentration.46 After the HEC reached steady state determined from the constant particle mass loading from SMPS and AMS measurements, aerosol particles were collected on Teflon filters (Sartorius, 11807-47N) at a flow rate of 5 L min−1 for up to 48 h based on the particle production. The consistency of functional groups based on IR analysis of samples from different collection periods suggested the stability of collected samples on the filter for the given collection period. The samples were stored in the refrigerator at 4 °C prior to analysis within several days. Control studies using the infrared spectra of fresh compared to the stored samples showed the stability of such secondary organic material for at least 1 week under room temperature. Three types of aerosol particles were studied including (Table 1): (I) 300 ppb of isoprene mixed with 18−20 ppm H2O2 in the presence of 30-nm dry ammonium sulfate seeds under ultraviolet irradiation; (II) as with sample I but without sulfate seeds; and (III) 300 ppb of α-pinene mixed with 90 ppb of ozone in the dark. No NOx was added in these experiments, and the measured NOx concentration was 90%). After two cycles, the spectral response had better consistency upon further RH cycling. The time response of the spectra to a switch of dry-to-wet or wet-to-dry was less than 1 min. After three dry-wet cycles, the RH of the air flow was begun for RH > 95% and steadily decreased at 2% min−1 to RH < 5%. After remaining at RH < 5% for 10 min, the RH was cycled up at 2% min−1 to RH > 95%. The known spectral variation for the hygroscopic response of pure ammonium sulfate was used to confirm the accuracy of the in situ RH.

Figure 2. Infrared spectra of different films I−III of secondary organic material as experiment and ammonium sulfate as reference for 90% RH. The inset plots show the peak fitting results for Lorentzian functions in the region 1550−1900 cm−1. The black line represents the experimental data, and the red line shows the sum of the fitted peaks. The spectra are offset for clarity. The scales of the ordinates of the panels differ because of variability in the quantity of organic material transferred to the ATR element crystal and because of differences in water uptake with humidity.

3. RESULTS AND DISCUSSION The IR absorption characteristics of the films of secondary organic material are summarized in section 3.1. The influence of ozone exposure and ultraviolet irradiation on the sample films is discussed in section 3.2. Hygroscopicity of the films is addressed in section 3.3. 3.1. Infrared Absorption Characteristics. 3.1.1. Isoprene-Derived Material. Figure 2 shows the IR spectra for samples I and II (i.e., with and without sulfate seed particles) for isoprene and sample III for α-pinene, for both low and high RH. Also shown as a control study are results for ammonium sulfate. For samples I and II, the IR absorption characteristics are similar for both samples, suggesting that the applied sulfate seed particles have no detectable impact on organic composition in current experimental conditions. The IR absorption by ammonium and sulfate anions (i.e., bottom panel) is not detected because of the low relative concentrations (i.e., sulfate-to-organic mass ratios of less than 1% in this study). The absorption for 1550−1900 cm−1 is described by a Lorentzian function having a peak at 1720 cm−1 for RH < 5% and at 1650 cm−1 for RH > 90%, as shown by the inset plots. At low RH, the carbonyl absorption at 1720 cm−1 dominates. At high RH, strong water absorption at 1650 cm−1 obscures this smaller peak. The functional groups associated with specific IR absorption bands, excluding the general C−H or C−C absorption bands that are common to organic species, are summarized in the Supporting Information.51 C−H stretching occurs at 2850− 3000 cm−1, C−H deformation at 1350−1480 cm−1, and C−C stretching at 1120−1250 cm−1. As shown in Figure 2, both samples I and II have their strongest absorption in the 2700−

3600 cm−1 region, which arises from the O−H intermolecular and intramolecular hydrogen bonds, mainly from alcohols, alkyl peroxides, and water.51 Carbonyl absorption occurs as the peak at 1720 cm−1, with a half-width of 100 cm−1. The broad absorption across the 900−1500 cm−1 region includes C−H deformation for 1350−1480 cm−1, C−C stretching for 1120− 1250 cm−1, C−O stretching in various regions for different products, possible OH bending for peroxy acids, and possible O−H in-plane deformation for alcohols. The strong O−H stretching for 1000−1200 cm−1 suggests the presence of high concentrations of alcohol groups, in agreement with reports based on mass spectrometric analysis.52−54 In the 1000−1200 cm−1 region, the absorption is associated with O−H in-plane deformation, suggesting that primary alcohols are dominant (i.e., −CH2OH groups). Also possible, however, is that significant concentrations of peroxy acids or alkyl peroxides are present because the C−O stretching bands of these species give rise to strong absorption over 1050−1100 cm−1. The nondetectable nitrate related absorption51,55 such as 1610− 1660 cm−1, confirms the low NOx experimental condition. The oxidation of isoprene with OH radicals at low NOx conditions is expected to form first-step gas phase species such as methylbutenediols, hydroxyhydroperoxides (ISOPOOH), hydroxycarbonyls, methacrolein (MACR), and methyl vinyl 110

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carbonyl species. There is also broad absorption from 1000 to 1500 cm−1, associated as for samples I and II, with C−H deformation and stretching, C−C stretching, and possible OH bending for peroxy acids or O−H in-plane deformation. The possible composition for sample III therefore includes carboxylic acids, aldehydes, ketones, esters, and peroxy acids, with the spectral evidence showing a dominance of carboxylic acids. 3.1.3. Absence of Detectable Organosulfates. The production of sulfate esters accompanying the oxidation of volatile organic compounds in the presence of inorganic sulfur species has been reported using chromatographic analyses, such as by Surratt et al.,63,64 Iinuma et al.,61,65 and Liggio et al.66,67 Due to the complexity of SOM, however, the composition of SOM cannot be completely illustrated using a single technique, and in comparison to chromatography the present technique of ATR-IR allows the characterization of functional groups without solvent extraction. In the infrared spectrum, organosulfates have contributions by the SO vibration at 1210− 1260 cm−1, the COS vibration at 770−810 cm−1, and the CO portion vibration of COS link at 1030−1050 cm−1.68,69 The absorption signatures of sample I (i.e., with seeds) and sample II (i.e., without seeds) are similar (Figure 2). The conclusion is that the major absorption bands of organosulfates do not appear in the spectra, indicating an absence of detectable organosulfates. Possibilities are (1) that the production of organosulfates is negligible for the employed experimental conditions because the current sulfate seeds are not acidified.53,58 (2) that the absorption by organosulfate functionalities overlap with the absorption of other functional groups, or (3) that the ammonium sulfate fraction of 1% in the overall particle yields are too low for spectroscopic detection and also the applied sulfate mass loading is only 0.6% of most other organosulfate studies.53,58 Other experimental conditions, such as higher concentrations of sulfate seeds or more acidic conditions, might increase organosulfate production and thereby assist in spectroscopic detection to quantity the physical properties because they are observed in both chamber studies and field measurements.53,58,63,64,70 3.2. Photolysis. The sample films (I and III) are exposed to two types of aging processes, including (1) additional ozone exposure (Figure 3) and (2) prolonged ultraviolet irradiation at 254 nm (Figures 4 and 5). Additional ozone exposure leads to no significant changes in the infrared spectra, indicating that the studied secondary organic material consists mostly of saturated organic species inert to additional ozone exposure, at least for the applied ozone exposures. The exposures are equivalent to 3.8 days for a representative atmospheric concentration of 50 ppb ozone. The lack of reactivity over ozone also suggested the quantity of the reported product, unsaturated C5-alkenetriols derived from the oxidization of isoprene is low in contrast with other saturated products for the applied experimental condition or the reactivity of such unsaturated products is not significant for the applied ozone dose. Figure 4 shows the time series of spectra for samples I and III exposed to 254 nm irradiation. For sample I of the isoprenederived material, most absorption bands decrease significantly with irradiation. After 25 min of radiation, the O−H and C−H stretching bands decrease by 30%. The C−O stretching band at 1045 cm−1 decreases by 50%. An exception is carbonyl absorption, which at first increases and then subsequently decreases with irradiation time. The band intensity reaches a maximum value of 160% compared to the original intensity

ketone (MVK) before forming other gas phase species or aerosol phase products.56,57 ISOPOOH is reported to have more than 70% yield among the first-step products and further converted to form dihydroxyepoxides (IEPOX) which form C5-alkenetriols, 2-methyltetrols, and IEPOX-derived higher order oligomers56−58 without acid catalysis. The reported IEPOX derived species are usually composed with multiple hydroxyl groups without carbonyl and contribute mainly on the O−H stretching in the 2700−3600 cm−1 region. The significant high absorption of O−H at low relative humidity can provide a possible tracer for the SOM derived from oxidation of isoprene with OH at low NOx condition. In addition to the strongest absorption in the 2700−3600 cm−1 region by O−H, the significant carbonyl absorption shown in Figure 2 thus suggests the presence of C5-alkenetriols in aldehyde or ketone form or the importance of other pathways through carbonyl related first-step oxidation products such as hydroxycarbonyls, MACR and MVK to the form carbonyl related products, which might be sensitive to the applied detection methods. 3.1.2. α-Pinene-Derived Material. Figure 2 for sample III shows that, in comparison to the spectra of samples I and II, the relative intensity of O−H or OO−H of sample III is weaker and red-shifted to 3200 cm−1 for 90%. As shown by the fit, even in the presence of significant absorbed water, the carbonyl absorption is resolvable. The hygroscopic response results mainly from the interaction of water with the 111

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Figure 3. Infrared spectra of the films of secondary organic material before exposure to ozone as well as the difference spectra after exposure. (A) Sample I: isoprene. (B) Sample III: α-pinene. Conditions: 52 ± 2% RH and 18 ± 1 ppmv O3 for 15 min.

Figure 5. Time response of the absorption ratio A(t)/A0 of selected bands for increasing exposure to ultraviolet radiation. The term A0 is the absorption intensity prior to exposure, and the term A(t) is the absorption some time t later. (a) Sample I: isoprene. (b) Sample III: αpinene. The fitting functions for the indicated wavenumber regions are inset into each panel. The red lines are the fitting results. Conditions: 90%, the curves of A3385 and xW_CO differ significantly for the hydration and dehydration branches, especially for samples I and II. The explanation might be the droplet size varies rapidly at high RH as stated in section 3.3.1, with different implications for the two branches. For dehydration, the sample is initially exposed to RH > 95% for 10 min. In this case, samples I and II can take up sufficient water to possibly have a flat surface. Once the RH decreases, the flat film starts to evaporate and break into small droplets, with stronger curvature effects for the initial evaporation process. The implied result is an inconsistency of absorption ratio between the two branches for the high RH region. Such deviation is less significant for sample III possibly due to the lower initial RH and different hygroscopicity than samples I/II lead to less flat droplets initially. The absorption ratios xW_CO of samples I/II/III and oxalic acid (OA) are listed in Table 2 for four RH conditions (20%, 40%, 60%, and 80%). The ratios for oxalic acid serve as a benchmark for hygroscopicity that is contributed mainly by carboxylic acid groups. The xW_CO values of sample III are within a factor of 2 of the benchmark, suggesting that carboxylic acid groups produced in large yield by ozonolysis reactions dominantly contribute to water uptake. By comparison, the xW_CO values for samples I and II are several times higher than the benchmark, indicating that in the case of isoprene-derivedmaterial there is a broader group of species contributing to hygroscopicity. This result is consistent with the strong O−H composition (i.e., alcohols and peroxides) identified in the infrared spectra (Figure 2). Noncarbonyl species then play a major role for the hygroscopicity of SOM produced through OH oxidation.

isoprene with hydroxyl radical and α-pinene with ozone at low NOx conditions were studied using attenuated total reflectance infrared spectroscopy. The films were highly oxidized and nonreactive to further ozone exposure, yet they were still reactive to additional ultraviolet irradiation possibly due to the presence of organic peroxides. Using the hygroscopic response of oxalic acid as a benchmark, a significantly higher ratio xW_CO, representing the intensity of the water-bending peak to that of carbonyl absorption, was recorded for isoprene-derived material. This result suggests that the hygroscopicity of the isoprenederived film under low NOx condition arose in large part from species other than carbonyl groups, such as alcohols and possibly peroxides. In comparison, the ratio xW_CO for αpinene-derived material was similar to that of the benchmark, suggesting that carbonyl-related species, specifically carboxylic acids, were the dominant contributor to hygroscopicity. For the irradiation experiments, the photo channels produce additional hygroscopic carbonyl species, and as such these reactions under atmospheric conditions might be an important pathway of reactive aging to produce hygroscopic carboxylic acids, in complement to the initial chemistry such as ozonolysis of the unsaturated organic compounds and other pathways.

4. CONCLUSIONS The functional groups and hygroscopic properties of films of secondary organic material produced by the oxidation of

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ASSOCIATED CONTENT

S Supporting Information *

Summary of the IR absorption of selected functional groups.51 This information is available free of charge via the Internet at http://pubs.acs.org.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS Funding for this research was provided by National Science Council of Taiwan (97-2111-M-002-008-MY3). This material is based upon work supported by the National Science Foundation under Grant No. 0925467. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. We thank Soeren Zorn, Mikinori Kuwata, and Yue Zhang for technical assistance in the production and collection of secondary organic material from the Harvard Environmental Chamber. All the constructive comments and suggestions from reviewers are truly appreciated.



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