Changes to the chemical composition of soot from heterogeneous oxidation reactions
The atmospheric aging of soot particles, in which various atmospheric processes alter the particles\' chemical and physical properties, is poorly understood and consequently is not well-represented in models. In this work, soot aging via heterogeneous oxidation by OH and ozone is investigated using an aerosol flow reactor coupled to a new high-resolution aerosol mass spectrometric technique that utilizes infrared vaporization and single-photon vacuum ultraviolet ionization. This analytical technique simultaneously measures the elemental and organic carbon components of soot, allowing for the composition of both fractions to be monitored. At oxidant exposures relevant to the particles\' atmospheric lifetimes (the equivalent of several days of oxidation), the elemental carbon portion of the soot, which makes up the majority of the particle mass, undergoes no discernible changes in mass or composition. In contrast, the organic carbon (which in the case of methane flame soot is dominated by aliphatic species) is highly reactive, undergoing first the addition of oxygen-containing functional groups and ultimately the loss of organic carbon mass from fragmentation reactions that form volatile products. These changes occur on timescales comparable to other non-oxidative aging processes such as condensation, suggesting that further research into the combined effects of heterogeneous and condensational aging is needed to improve our ability to accurately predict the climate and health impacts of soot particles.
Introduction<!>VUV-SP-AMS<!>Flow tube set-up<!>Composition of unoxidized soot<!>Chemical changes resulting from OH oxidation<!>Chemical changes resulting from ozone oxidation<!>Atmospheric implications and future work
<p>Particulate and gaseous emissions from the incomplete combustion of fossil fuels, biofuels, and biomass are known to have important influences on both climate and human health.1,2 An important component of such emissions are strongly light-absorbing carbonaceous particles ("soot"), which have recently received substantial attention due to their uncertain and potentially large climate impact.3–6 Soot particles, containing a mixture of graphitic sp2-bonded carbon (elemental carbon) and other co-emitted and internally mixed particulate organic and inorganic species, can have a dramatic influence on climate due to their strong absorption of light in the visible and ultraviolet regions of the electromagnetic spectrum. By some estimates, the climate warming by soot particles is second only to CO2;4 however, this is highly uncertain, with estimates for direct radiative forcing ranging from 0.17 W m-2 to 0.9 W m-2.3,4,6–9</p><p>This wide range in estimated climate impacts is partly due to uncertainties associated with the atmospheric lifetime of soot.4–6,9. Soot lifetime is governed primarily by its wet deposition rate8,10 and is thus determined by the particle surface's affinity for water (hydrophilicity). Since soot particles from many sources (e.g., fossil fuel combustion) tend to be initially hydrophobic when emitted,4 atmospheric "aging" processes that increase the water-uptake properties of soot particles can play a major role in determining their atmospheric lifetimes. The parameter typically used to model such processes is the hydrophobic-to-hydrophilic conversion rate (hereinafter referred to as "conversion rate") of soot, which has been shown to have a controlling influence on the lifetimes and hence atmospheric burdens of soot particles. For example, in a sensitivity study by Koch et al.,5 increasing the conversion rate by a factor of two resulted in a 19% decrease in modeled soot burden, while a rate a factor of two slower increased the modeled burden by 42%, thus indicating the importance of this conversion rate to the loading, and ultimately the overall climate impact, of soot particles.</p><p>The chemical and physical processes responsible for the conversion of soot from hydrophobic to hydrophilic include coagulation with other particles, condensation of gas-phase organic and inorganic species, and heterogeneous oxidation of the particle surface. Partly due to a lack of comprehensive and systematic laboratory studies on the rates of these chemical processes, global models have typically used conversion rates tuned to make modeled and measured soot concentrations match.11,12 Traditionally, many global models have used fixed values for this rate;5 however, as ambient observations increase in number, it has become apparent that a fixed value is insufficient to capture the seasonal, regional, and vertical variability of soot concentrations.9,13–15 Consequently, more recent models have included improved treatments of conversion rates by explicitly modeling the coating of soot by secondary compounds, namely H2SO4,9,14,16,17 or by parameterizing different aging processes for fossil-fuel and biomass-burning soot.9 Although these more detailed treatments of the conversion rate typically perform better than fixed-rate assumptions,9,14,16,17 measurement-model disagreements persist, indicating a specific need for a more thorough understanding of the processes that govern the water-uptake properties of soot particles.</p><p>Aging via heterogeneous oxidation of soot surfaces by gas-phase oxidants is one of the more uncertain soot aging processes. Most previous laboratory work on heterogeneous soot oxidation has focused on oxidation by ozone only. These studies have examined the kinetics of ozone uptake,18–24 the rates of degradation and product formation of polycyclic aromatic hydrocarbons (PAHs, components of the soot organic carbon known to have carcinogenic and mutagenic effects),25–28 and the changes to the particles' water uptake properties.29–32 The heterogeneous oxidation of soot by the hydroxyl radical (OH) has received far less attention.24,33–36 To our knowledge, the chemical changes to the soot surface have not been previously examined, although one study33 has found an increase in the water uptake of oxidized soot relative to the unoxidized soot. Overall, there exists little information on the kinetics and the condensed-phase products of the reaction of OH with soot particles, limiting our ability to assess the role of heterogeneous oxidation in soot aging. In order to improve our understanding of this aging process, here we characterize the chemical changes that the organic and elemental carbon fractions of soot undergo upon heterogeneous oxidation by OH and ozone, using an aerosol flow reactor to oxidize the soot particles and a novel aerosol mass spectrometric technique to monitor their composition.</p><!><p>In this paper, soot chemical composition is characterized using a new technique for the measurement of both the organic and the elemental carbon fractions of the particles, involving a modified version of the Aerodyne soot particle aerosol mass spectrometer (SP-AMS).37 The SP-AMS is a high-resolution time-of-flight aerosol mass spectrometer38,39 that uses a 1064 nm YAG laser to vaporize refractory elemental carbon and non-refractory species associated with the elemental carbon. In the standard SP-AMS configuration, ionization of the vapor is achieved using electron impact (70 eV); in these experiments we instead use vacuum ultraviolet (VUV) single-photon ionization, utilizing VUV light from the Chemical Dynamics Beamline (9.0.2) of the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory. This specific configuration is described in detail elsewhere.40 Briefly, this combination of IR vaporization and VUV ionization requires that three beams – the laser, VUV light, and particle beam – all intersect within the ionization region of the mass spectrometer. The laser enters the ionization region perpendicular to the particle beam while the VUV enters from the back of the ionizer cage via a custom back flange 20° off center. This configuration necessitates the use of the large ionizer cage and removal of the thermal vaporizer.</p><p>Using VUV-SP-AMS allows for the sensitive monitoring of the chemical changes to organic compounds within the soot, which (as shown below) are far less abundant yet more reactive than the elemental carbon cores. Since ionization cross sections increase with increasing photon energy, this technique has a higher sensitivity to the organic carbon (ionization energies of ∼7.4-11 eV41), than to the elemental carbon (ionization energy 11.6 eV for C3,42 the most abundant carbon cluster formed in the vaporization of elemental carbon). While tunable VUV radiation is available at the ALS, the present results focus on ionization at 12 eV only, allowing for the simultaneous measurement of the elemental and organic carbon while maintaining the enhanced sensitivity to organic species. Elemental and organic carbon are determined from their exact masses and ion formulae using high-resolution analysis of the low-mass ions (m/z < 130); due to the presence of numerous possible isobars at higher m/z (particularly at high oxidant exposures), the treatment of the mass spectrum at high m/z is mostly restricted to unit mass resolution. This choice does not affect the interpretation of the results because ions with m/z < 130 represent the majority of the signal for both the elemental and organic carbon (discussed in further detail in the Results section).</p><!><p>Aging experiments were carried out in an oxidation flow reactor, previously developed for studies of the heterogeneous oxidation of organic particles;43–45 the primary modification for the present study was the method of particle introduction, involving aerosolization of a suspension of flame soot in water. Flame soot generated from the fuel-rich combustion of methane in an inverted co-flow diffusion flame 46 was collected on filter paper and extracted with water using sonication. The resulting suspension underwent continuous sonication as it was atomized with a constant-output atomizer (TSI) using N2 gas; particles were then passed through a diffusion dryer, and combined with the carrier flow (0.57 SLM of 17% O2 in N2 at ∼30% RH). This flow was combined with 0.05 SLM flow of ozone in N2/O2 and 0.025 SLM of a hexane mixture (∼5 ppm in N2) to result in a total flow of 1 SLM through the flow tube. OH radicals were generated within the reactor via the 254 nm photolysis of ozone and subsequent reaction of O(1D) with water. Exposure to the 254 nm radiation only (with no ozone addition) resulted in no measurable changes to the soot particles. Different OH exposures were achieved by modifying the ozone concentration in the flow tube; residence time in the flow tube remained constant at ∼37 s. Ozone only (lights off) experiments were also done using similar concentrations of ozone as used in the OH experiments. The OH exposure was quantified by measuring the decay of hexane (initial mixing ratio of ∼125 ppbv) using gas chromatography with flame ionization detection (GC-FID). GC-FID measurements are available for about half the experiment; OH exposure for the remainder of the experiment was estimated using a regression derived from measured hexane and ozone concentrations from an experiment performed the same day over a similar ozone concentration range. Particles exiting the flow tube were sent to a scanning mobility particle sizer (TSI model 3080), for quantification of particle number and electrical mobility diameter, and to the VUV-SP-AMS, for measurements of chemical composition. Averaged over the course of the experiment, the SMPS-derived surface-area weighted geometric mean diameter of the soot was 155 nm, with a volume loading of 1.55 × 108 μm3/m3.</p><!><p>The unoxidized mass spectrum of the flame soot is shown in Fig. 1. For the purposes of this study, the elemental carbon core of the soot is determined from the sum of the high resolution ion intensities of the elemental carbon ions (formula Cx+, where x is an integer from one to ten). Higher-mass Cx+ ions are present in low abundances, with the total signal from the C11≤x≤25+ ions accounting for only 7% of the total Cx ≤ 10+ signal. This represents an upper limit, due to the increasing likelihood of isobaric organic ions that are difficult to resolve at these high masses. The most abundant elemental carbon ion is C3+, accounting for 55.3 ± 0.6% (mean ± 1σ) of the signal. The high abundance of C3+ is consistent with previous studies at 70 eV.37,47,48 C1+ accounts for 10.2 ± 0.6% of the signal, C2+ is 11.8 ± 0.3%, C4+ is 8.0 ± 0.2%, and C5-10+ is 14.7 ± 0.5% of the signal. Since this Cx+ fragmentation pattern was obtained via ionization at 12 eV, it is not directly comparable to the Cx+ fragmentation pattern obtained when using electron impact ionization at 70 eV; these differences are explained in detail in a separate study.40</p><p>For unoxidized soot (Fig. 1a) the total intensity of the organic ions is similar to that of the Cx+ ions, with the organic ions accounting for 62% of the m/z < 130 signal. Due to the higher sensitivity of VUV-SP-AMS to the organic carbon compared to the elemental carbon, these similar intensities do not imply similar abundances. In fact, as discussed in detail below, the organic carbon accounts for a small fraction of the soot mass (on the order of a few percent), consistent with previous measurements from this flame source.46</p><p>The organic carbon spectrum of unoxidized soot, shown in greater detail in Fig. 1b, is predominantly composed of low-mass fragments, with high-mass ions (m/z ≥ 130) representing only 30% of the organic signal. Based on high-resolution analysis, the organic fraction is dominated by reduced aliphatic hydrocarbons; ions typical of aromatic species (which typically have formulae of CnH0.5n+ to CnHn+ or C6H5(CH2)n+)49 account for <1% of the low m/z organic signal and oxygenated ions account for 5%. (Fig. 1b). Since VUV ionization efficiency is highly sensitive to the class of chemical compound (alkane, aromatic, etc.),50 these contributions are not strictly equivalent to mass fractions within the particles. However, VUV ionization cross-sections of aromatics are generally larger than those of aliphatic species50, implying that the organic species are predominately aliphatic in nature.</p><p>The total organic signal is primarily made up of ions of the form CnH2n+1+ (32% of the CxHy+ ions) and CnH2n-1+ (35%). Other important ion series include CnH2n+ and CnH2n-2+, which account for 19% and 10%, respectively, of the CxHy+ signal. These less-hydrogenated ions are typical for fragments of aliphatic unsaturated hydrocarbons (with double bonds or rings). The ions at higher masses (identified using unit mass resolution) exhibit the same characteristic groupings spaced by 14 units out to about m/z 200. At higher masses (m/z > 200), specific high molecular-weight ions become prevalent. These include m/z 202 and 216; high resolution analysis indicates that at least part of these signals are due to the ions C16H10+ (Fig. S1) and C17H12+ (Fig. S2), which correspond to polycyclic aromatic hydrocarbons (PAHs). An aliphatic ion at m/z 280 (C20H40+) is also prominent (Fig. S3). The ion signal at m/z 252 (Fig. S4) includes contributions from both C20H12+ (corresponding to a PAH) and the C18H36+ (an aliphatic ion).</p><p>The continuous sonication of the soot, necessary to ensure a steady atomizer output and to prevent the atomizer from clogging, may result in changes to the soot composition.51 To investigate this, we analyzed an unoxidized mass spectrum at the beginning of the experiment and a second unoxidized spectrum obtained about halfway through the experiment. These two mass spectra, both normalized to the Cx+ signal, exhibit small changes in ion intensities. Compared to the first mass spectrum, the second shows a slight increase in oxygenated ions (up from 5% to 6% of the signal for m/z < 130) and in low-mass hydrocarbon ions (e.g., C4H9+ increases by 14%), whereas it shows a decrease in the high-mass hydrocarbon ions (e.g., m/z 280 – primarily C20H40+ – decreases by 13%). The PAH signals at m/z 202 and 216 show a disproportionately larger decrease than the aliphatic ions (m/z 202 decreases by 19%). Due to uncertainties regarding the effect of sonication on the PAHs over the course of the oxidation experiment, we do not attempt to quantify the oxidation of the PAHs.</p><p>The changes to the aliphatic ions resulting from sonication are smaller than the change observed from the lowest non-zero OH exposure (discussed in detail below), and thus sonication has a negligible impact on the interpretation of the OH oxidation of the aliphatic organic species. The changes observed during the ozone oxidation experiments (described below), which are more subtle, are comparable to the overall changes resulting from sonication; however, assuming that the changes arising from sonication occur linearly with time, the effects of sonication is expected to be small over the limited duration (∼30 min) of the ozone experiment. Thus, the changes to soot particle composition as a result of sonication can be neglected when examining the chemical changes resulting from either OH or ozone oxidation.</p><!><p>Over the range of oxidation conditions used here (maximum OH exposure equivalent to ∼13 days of atmospheric exposure, assuming an atmospheric concentration of 106 molecules cm-3), the mass spectrum of the elemental carbon (Cx+) remains invariant. The Cx+ signal also correlates well with the integrated volume from SMPS scans across all oxidation conditions (R2 = 0.91) and the SMPS-derived average volume per particle shows no trend with OH exposure (R2 = 1 × 10-5) despite large changes in the total organic signal (discussed below). This implies that the soot is primarily composed of elemental carbon (consistent with previous characterization of soot from this flame source)46 and that the elemental fraction of the particles is inert to oxidation under atmospherically relevant oxidant exposures. It also constrains the volume fraction of organic carbon in the soot to be similar to, or less than, the observed variation between subsequent SMPS measurements of integrated volume. This variation is, on average, 3% and results from both the stability of the atomizer and the reproducibility of SMPS scans.</p><p>In contrast to the elemental carbon fraction of the soot, the organic fraction undergoes dramatic changes upon oxidation; Figure 2 shows the evolving organic mass spectrum at various levels of OH exposure. All organic signals have been normalized to Cx+ to account for atomizer output fluctuations. Since the changes resulting from ozone oxidation (discussed below) were much smaller than those observed for OH, no correction for oxidation by ozone is needed. OH oxidation increases the abundance of oxygenated ions (CxHyO+ and CxHyOz+, where z>1) and decreases the total abundance of the ions containing only carbon and hydrogen (CxHy+), consistent with previous AMS studies of the heterogeneous oxidation of organic aerosol.45,52 Inspection of the CxHy+ trend with oxidation indicates that while some of the ions continuously decrease with oxidation, others increase during the initial stages of oxidation. The CxHy+ ions that decrease with oxidation follow the formula CnH2n+1+ and CnH2n+ with n=4-9, and CnH2n-1+ and CnH2n-2+ with n=6-9; we refer to these as "reactant-CxHy+." The ions that increase with oxidation ("product-CxHy+") follow the formula CnH2n+1+ and CnH2n+ (n=2-3), CnH2n-1+ (n=2-5), CnH2n-2+ (n=4-5), and CnH2n-3+ (n=5-9). "Remainder-CxHy+" contains all other ions with the formula CxHy+. All the ions within this last group have a lower hydrogen-to-carbon ratio (H/C) than those in the reactant- or product-CxHy+ groups, and either remain constant or increase with oxidation. While this is initially a small fraction of the total, its importance as a fraction of total CxHy+ increases as oxidation proceeds and the total CxHy+ intensity decreases.</p><p>At low oxidation levels, up to the equivalent of about two days of oxidation (assuming an average OH concentration of 106 molecules cm-3), the total organic signal increases due to the increasing levels of the oxygenated ions. Since it is possible that the VUV ionization cross-sections are different for oxygenates than for the reduced hydrocarbons, this does not necessarily imply an increase in organic mass; however, it is clear that the oxygen content of the organic species increases with oxidation. This change is also reflected in the formulae of the product-CxHy+ ions, which generally have a lower hydrogen content and/or smaller carbon numbers than the reactant-CxHy+ ions. Although lower H/C values can indicate increasing levels of unsaturation, here they are likely to be fragments of the oxidized organic molecules that have undergone oxygen loss in the vaporization or ionization steps. This observation of increases in CxHy+ ions with low H/C has also been observed by Kroll et al.53 for the heterogeneous oxidation of diesel exhaust aerosol. The lower H/C and general increasing trend of the remainder-CxHy+ ions suggests that these ions may also be the result of the fragmentation of oxygenates.</p><p>As the oxidant exposure increases, all ions attributed to oxygenates (including the product-CxHy+) reach a maximum and then begin to decrease, with the CxHyOz+ signal peaking at noticeably higher OH exposures than either the product-CxHy+ or the CxHyO+ signal. This behavior is consistent with the evolution of multiple generations of oxidation products: early generations involve the addition of oxygen-containing functional groups, whereas later generations are characterized by increased fragmentation that results in the loss of mass via the formation of small, volatile products.45,54</p><p>The effective rate of oxidation of the reduced organic molecules can be determined by fitting the decay in the reactant-CxHy+ signal. The fit is restricted to include only the points at OH exposures of < 9.5 × 1010 molecules s cm-3, for which measurements (rather than estimates) of OH exposure are available. This results in an effective second-order oxidation rate constant of the soot organic fraction by OH of 7.9 ± 0.2 × 10-12 cm3 molecules-1 s-1, equivalent to a lifetime of 1.5 days in the atmosphere (assuming a diurnally averaged OH of 106 molecules cm-3). Since this rate is determined from the decay of many ions, it represents an average rate for the reaction of the various organic species, and is thus necessarily slower than the rate of the fastest-decaying ion. However, although all the reactant-CxHy+ ions exhibit a decrease with increasing oxidant exposure, some of these ions may arise from fragmentation of high molecular weight oxygenates during vaporization or ionization. Inspection of various ions of relatively high abundance and high-resolution analysis of m/z 280 indicates that for individual high m/z ions the oxidation rate of may be up to a factor of two faster. We emphasize that this is an absolute upper limit and that the average rate for all the organics will be lower.</p><p>The CxHy+ decay expected from this rate is shown extended out to higher oxidation levels in Fig. 3. For oxidant exposures up to ∼4 × 1011 molecules s cm-3 (4.6 days), there is good agreement between the expected decay and the CxHy+ measurement; however, at higher oxidation exposures the measured ion intensities begin to plateau at a non-zero value. This result may indicate that some fraction of the hydrocarbon is inaccessible to oxidation, possibly due to soot morphology. Often referred to as "shielding" of the organic species from oxidation, this phenomenon has previously been proposed to explain concentrations of soot-associated PAHs in remote regions that are inconsistent with laboratory measurements of PAH oxidative lifetimes.55–57 Alternatively, this apparent plateau may be the result of the remaining organic species having a greatly reduced oxidation rate compared to those that reacted away initially.</p><p>The second-order rate constant can be used to calculate the initial uptake coefficient, γ OH, defined here as the fraction of collisions of OH with soot particles that lead to reactive loss of reduced hydrocarbons:</p><p>Here k is the second-order reaction rate constant, –c is the mean speed of the OH molecules (619 m s-1), and S is total aerosol surface area per unit volume (cm2/cm3). Most treatments of the heterogeneous oxidation of organic aerosols assume the entire mass of the particle is reactive and thus the reactive organic mass is proportional to the particle volume.43,44,53,58 Such an assumption is not valid in the present case, since most of the particle mass is non-reactive elemental carbon. Instead, the reactive organic carbon is present as a thin coating, and is therefore better described in terms of the particle surface area:</p><p>where x is the surface area coverage of the organic molecules (molecules cm-2). Substitution of Eq. 2 into Eq. 1 yields:</p><p>Assuming a coating thickness of 1 nm and a density and molecular weight typical for a C8 alkane/alkene (0.7 g cm-3 and 114 g mol-1) results in a surface area coverage (x) of 3.7 × 1014 molecules cm-2 and an uptake coefficient (γOH) of 0.19. Due to uncertainties regarding the surface area coverage of organic species, which is complicated by the uncertain morphology and homogeneity of organic species distribution on a given soot particle, this number is not corrected for gas-phase diffusion; doing so would result in a 5% increase in the uptake coefficient. This calculation is also sensitive to the assumptions regarding coating thickness, density, and molecular weight. The coating thickness assumed above is consistent with the constraints on the organic volume fraction from the SMPS: a 1 nm coating thickness is equivalent to a volume fraction of 4%, assuming a spherical particle with a diameter of 155 nm (the surface-weighted mean diameter of the soot). Due to the large degree of organic fragmentation observed, it is difficult to constrain the density and molecular weight of the organic species. As an upper limit, we assume a C20 molecule (consistent with the peak observed at m/z 280) with a density of 0.8 g cm-3 and the same coating thickness. This results in a surface area coverage (×) of 1.7 × 1014 molecules cm-2 and an uptake coefficient (γ) of 0.09.</p><p>The γOH derived here is broadly consistent to previous determinations for methane flame soot: Bertram et al.24 report a range of 0.5 to 1 (average of 0.88) using a coated flow tube approach while Park et al.34 report a larger range of 0.03 to 1 using a bead-filled flow tube. Differences between these values may be due to differences in the organic composition of the soot in the different experiments, though they also may arise from errors in the determination of surface characteristics (surface area or surface coverage) in the various experiments. The value of γOH derived here also agrees to within a factor of two of past measurements of γOH for squalane, a C30 branched alkane.43</p><!><p>Due to the short residence time in the flow tube (37 s) and the fact that ozone is present in the atmosphere at concentrations on the order of tens of ppbv, high ozone exposures (equivalent to several days in the atmosphere) could not be achieved. Instead, the maximum ozone exposure (3.1 × 1016 molecules s cm-3) corresponds to about 9 h in the atmosphere (at 40 ppbv ozone), a much lower equivalent atmospheric exposure than in the OH experiments. The change in the various ion classes (using the same definitions as with the OH exposure) as a function of ozone oxidation is shown in Fig. 4. The changes observed with ozone were much smaller than those for OH; changes at the highest ozone concentration (the same concentration used to achieve the highest OH exposure) were nearly equal in magnitude to those observed at the lowest non-zero OH exposure. This confirms the appropriateness of neglecting an ozone correction for the OH data presented above.</p><p>While the OH and ozone experiments differ in the magnitude of changes to ion intensities, the observed chemical changes to the soot in the two cases are similar; the reactant-CxHy+ and product-CxHy+ ions are the same as in the OH oxidation experiments and exhibit the same trends with increasing oxidation. Since ozone reacts with alkenes but not alkanes, this suggests the presence of alkenes. In addition to these two classes of ions, the CxHyO+ ions also show a minor increase. The remaining classes of ions show no discernible trend.</p><p>Fitting an exponential decay (with no constraint on the zero oxidation value) to the reactant-CxHy+ signal results in a second-order rate constant of 6 ± 1 × 10-18 cm3 molecules-1 s-1; including the zero-oxidation value in the fit increases the rate by 25%. This rate is equivalent to a lifetime of just under 2 days, assuming an ambient ozone concentration of 40 ppbv. This lifetime is comparable to that derived from the OH oxidation experiments, suggesting that the modest changes in the organic signal observed here are the result of low equivalent atmospheric exposures, and not from a lack of reactivity to ozone, and that the two oxidants are approximately equally efficient at oxidizing soot-associated organic species. The elemental carbon portion of soot is inert to oxidation by either oxidant.</p><p>The second-order rate, combined with the same set of assumptions as above for the aliphatic molecular weight, density, and surface coverage for a C8 molecule results in a γO3 of 2 × 10-7. This γO3 value is somewhat lower than those reported previously for oleic acid,59 self-assembled alkene monolayers,60,61 and soot,18,19,23,62 which are typically on the order of 10-6 to 10-3. Many of these studies, however, monitored only the ozone loss and the initial γO3 may be higher due to non-reactive ozone uptake on the surface; previous studies have reported that heterogeneous ozone loss occurs via a Langmuir-Hinshelwood mechanism, in which ozone first reversibly adsorbs to the surface before undergoing reaction.</p><!><p>This work shows that heterogeneous reactions with OH and ozone are efficient mechanisms for oxidizing aliphatic organic species present on soot particles. While the average timescales for such oxidation processes are on the order of 1-2 days, the detailed impact for a given particle will vary spatially and temporally due to variability in oxidant concentrations. For instance, the organic species on soot emitted in the late morning in a moderately polluted environment (with an OH concentration of 3 × 106 molecules cm-3 and 60 ppbv ozone) will have a lifetime of 8.5 hours, with the two oxidants contributing approximately equally to this reactivity. In contrast, soot emitted at night, when ozone concentrations are lower and oxidation by OH is negligible, will have a longer lifetime (> 30 h) with respect to oxidation. This lifetime is an upper limit given that the organic fraction of soot will also react with NO3.63</p><p>These heterogeneous oxidation timescales can be compared to the timescales of other soot aging processes, which have been primarily determined from atmospheric observations of soot coating, and model estimates of the relative importance of condensation versus coagulation. Particle-resolved models show diurnal trends in coating rates, with daytime aging resulting from condensation and occurring on the time scale of a few hours, and nighttime aging resulting mainly from coagulation and occurring on timescales closer to one day.64–66 Atmospheric measurements indicate similar trends with daytime coating occurring on the timescale of hours67–70 with faster coating timescales observed for soot from biomass burning and slower timescales for fossil fuel soot emissions.69,71,72 At night the coating rate is slower,70 consistent with the expected decrease in condensable gas production. Some atmospheric measurements, however, find that increasing plume age does not always result in increases in coating.71 Although this may in part be due to preferential scavenging of coated soot,71 it is also consistent with observations showing that biomass burning organic aerosol is semi-volatile and evaporates with aging72–75. Thus, the organic component of soot may remain exposed and subject to heterogeneous oxidation for extended periods of time.</p><p>These considerations suggest that heterogeneous oxidation of the organic fraction of soot occurs on timescales comparable to the coating timescales. It should be emphasized that the lifetime of the soot organic fraction is not necessarily equivalent to the lifetime for the hydrophobic-to-hydrophilic conversion of soot, particularly in cases where condensation and/or coagulation will render a fraction of the organic component of soot inaccessible to oxidation (although coating by organic species is also not necessarily equivalent to the hydrophobic-to-hydrophilic conversion rate). Nonetheless, heterogeneous oxidation will likely affect not only the primary soot organic fraction, but also condensed secondary organic species as well. In both cases, the heterogeneous oxidation of the organic fraction will alter how various gases (water, other inorganic and organic species) interact with the soot surface and thus will impact the overall soot aging.</p><p>The impact of heterogeneous oxidation on aging has been previously investigated using rates derived from the oxidation of PAHs by OH and ozone in a particle-resolved urban model76 and in global models assuming oxidation by ozone only.77–79 Such studies have generally found that although heterogeneous oxidation alone may result in the efficient oxidation of the surface PAHs,76 it becomes less important when condensation and coagulation are included as aging processes.77–79 To some extent, the reduced importance of heterogeneous oxidation as an aging mechanism in these studies results from the arbitrary reduction of the oxidation rate to some small fraction (often 1%) of its measured value, in order to account for "shielding" of the soot surface by condensed organic and inorganic species.78,79 This scaling can have a dramatic effect on soot lifetimes: Croft et al.78 found that changing this factor from 0.01 to 0.1 results in a decrease in the global mean lifetime of soot by almost 50% (from 9.5 days to 4.8 days) making it clear that better constraints on the relative roles of coating and heterogeneous oxidation are needed.</p><p>Overall, our results suggest that a more comprehensive treatment of heterogeneous oxidation of soot, including the oxidation of both aliphatics and aromatics by OH and ozone, is necessary to fully represent the aging process of soot. Due to variations in the abundance and composition of the organic carbon portion of soot,48,80 as well as variations in the quantity and composition of co-emitted species, the relative rates of condensation and heterogeneous oxidation as aging processes will likely exhibit strong temporal and spatial variabilities. To fully constrain these processes, soot aging experiments in which heterogeneous oxidation occurs in conjunction with the production of condensable gases (e.g., producing H2SO4 from the reaction of OH with SO2 in the presence of soot) are needed. Conducting these experiments with a wider range of soot sources (which will vary in the organic composition) and including simultaneous measurements of the hygroscopicity and/or CCN activity of the soot as a function of OH exposure, coating material, and coating thickness will significantly improve the understanding of the aging, condensational lifetime, and ultimately the climate and health impacts of soot particles.</p>