Persistence of organic carbon in heated aerosol residuals measured during Tropical Composition Cloud and Climate Coupling (TC4)



[1] The Particle Analysis by Laser Mass Spectrometry (PALMS) single particle mass spectrometer was used to analyze the composition of the nonvolatile fraction of atmospheric aerosol in a number of different environments. The mass spectra of individual particles sampled through an inlet section heated to 300°C were compared to unheated particles during flights of the NASA DC-8 aircraft during the Tropical Composition Cloud and Climate Coupling (TC4) mission. Comparisons are presented of measurements made in the marine boundary layer, the free troposphere, and the continental boundary layer over the Colombian jungle. The heated section completely removed sulfate from the aerosols except for sodium sulfate and related compounds in sea salt particles. Organic material in sea salt particles was observed to be less volatile than chlorine. Biomass burning particles were more likely to survive heating than other mixed sulfate-organic particles. For all particle types, there was a significant contribution to the residues from carbonaceous material other than elemental carbon. These results demonstrate the remaining compositional complexity of aerosol residuals that survive heating in a thermal denuder.

1. Introduction

[2] Online measurements of the volatility of atmospheric aerosols have been used to infer information about the composition of the aerosols and their mixing state [Moore et al., 2003; Villani et al., 2007]. Clarke et al. [Clarke et al., 1987; Clarke, 1991, 1993; Clarke et al., 1997, 2004, 2007] measured size distributions with optical particle counters with and without various amounts of heating. Thermal desorption coupled with a tandem differential mobility analyzer has been used to infer the composition of ambient nanoparticles [Sakurai et al., 2005] and larger mode particles [Orsini et al., 1999; Rose et al., 2006; Engler et al., 2007]. Thermal desorption studies also showed a higher fraction of nonvolatile material in freshly emitted vehicle combustion particles than in background aerosol [Philippin et al., 2004]. Several groups have also measured volatile and nonvolatile condensation nuclei (CN), although these measurements are not as relevant to the accumulation mode refractory composition measurements presented here because so little nonvolatile material is necessary to leave a core detectable by a CN counter.

[3] Following observations that organic compounds often comprise a significant fraction of fine aerosol mass [Novakov and Penner, 1993; Novakov et al., 1997; Murphy et al., 1998], volatility techniques have also been used to attempt to differentiate volatile sulfates and organics from nonvolatile elemental carbon [Smith and O'Dowd, 1996; Clarke et al., 2004; Howell et al., 2006]. The residual aerosol following heating to 300°C has been interpreted as elemental carbon [Clarke, 1993; Moore et al., 2003] and refractory organics [Smith and O'Dowd, 1996; Burtscher et al., 2001; Paulsen et al., 2006; Clarke et al., 2007]. This separation appears somewhat less clear than that of sulfate species. The processes by which organic compounds in a mixed aerosol evaporate are complicated by interactions between the different species [Brooks et al., 2002] and evaporation of organic carbon appears in some cases to be diffusionally limited [An et al., 2007]. Thus, variables such as particle composition and thermal denuder residence time can be significant when considering evaporation of volatile organic material.

[4] Direct analysis of the chemical composition of individual heated aerosol residuals allows more detailed and specific conclusions to be drawn than from typical volatility measurements that do not include composition measurements. For example, single particle mass spectra of ambient aerosols sampled through a thermal denuder have been reported for an urban environment with analysis focusing on the persistence, and possible increased formation, of oligomeric organic compounds in the denuder [Denkenberger et al., 2007]. Other groups have recently measured bulk aerosol mass spectra following thermal denuders using an Aerodyne Aerosol Mass Spectrometer (AMS) and found a significant fraction of organic mass in aerosols from different sources survived heating at temperatures up to 300°C [Huffman et al., 2008; Wu et al., 2009; Huffman et al., 2009a, 2009b]. Direct comparisons between studies are often difficult due to the different temperatures and residence times in the thermal denuders and the different capabilities of the mass spectrometers.

[5] We present results from direct measurements of heated aerosol residual composition by the Particle Analysis by Laser Mass Spectrometry (PALMS) single particle mass spectrometer aboard the NASA DC-8 during the Tropical Composition Cloud and Climate Coupling (TC4) mission.

2. Experimental Setup

2.1. TC4 Study

[6] The TC4 study (O. B. Toon et al., Planning and implementation of the Tropical Composition, Cloud and Climate Coupling Experiment (TC4), submitted to Journal of Geophysical Research, 2010) was conducted during July and August 2007 with research flights out of San Jose, Costa Rica. A map showing the flight tracks of the DC-8 science flights appears in Figure 1. The locations where aerosols were sampled through the heated inlet are indicated by circles on the flight track and are color-coded by aircraft altitude.

Figure 1.

Map of TC4 DC-8 flight tracks showing location of PALMS sampling through heated inlet (circles).

[7] To simplify the discussion of the data, we have aggregated the heated inlet data in three different regions: the marine boundary layer, the free troposphere, and the continental boundary layer over the Colombian jungle. The marine boundary layer is defined as altitudes less than 1500 m over the Pacific Ocean and the Caribbean Sea. The free troposphere category includes all heated sampling periods at altitudes over 6000 m. The differences between sulfate-organic particles in the tropics and midlatitudes were insignificant compared to the changes caused by heating, so they may be grouped together. The Colombian jungle boundary layer data consists of samples at altitudes less than 600 m during one flight. Together, these three regions account for 48 of the 68 heated sampling periods during the study. The remaining heated samples occurred mostly in the lower troposphere over Central America with a few low-altitude samples over North America.

2.2. Aerosol Sampling

[8] The ambient and heated residual particles for this analysis were sampled through the NASA Langley aerosol inlet. This inlet is the University of Hawaii inlet described in detail by McNaughton et al. [2007] in the results from the DC-8 Inlet Comparison Experiment. Flow from the inlet was split to a variety of aerosol instruments, including 0.7 L per minute (lpm) to the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument through approximately 2 m of 0.32 cm OD stainless steel tubing.

[9] For the analysis of nonvolatile residuals, the PALMS sample flow was switched with a four-way valve to take a portion of the inlet flow that had passed through a 40 cm long heated section of 0.635 cm OD (0.483 cm ID) tubing, temperature-controlled to 300 (±1)°C. The total heated flow rate of 1.7 L per minute (lpm) yielded a residence time of approximately 0.26 s within the heated region. Cabin temperature tubing downstream of the heated region acted as a sink for molecules volatilized from the aerosols to prevent recondensation onto the original aerosols. Laboratory tests by the Langley group have shown the heater to be 100% effective at evaporating 0.5 μm (NH4)2SO4 particles. Other laboratory tests showed that losses of nonvolatile particles in the accumulation size mode were in the range of 10–20% due to induced turbulence and thermophoretic diffusion within the heater.

[10] Some rough calculations of particle evaporation in the heater are informative. With some assumptions about molecular weight and diffusion coefficients, in 0.26 s at 300°C the majority of mass can be removed from a 0.5 μm diameter particle if the vapor pressure of the evaporating substance is on the order of 0.4 Pa or higher. Using the Clausius-Clapeyron equation and a latent heat of 150 kJ mol−1 [Chattopadhyay et al., 2001], this corresponds to species with room temperature vapor pressures above 10−13 Pa. As mentioned in the introduction, however, there may be other factors limiting the evaporation rate of organic aerosols. Oxidation of pyrolyzed organic particles on filters to release carbon to the gas phase takes minutes at temperatures of 300°C or even higher [Boparai et al., 2008].

2.3. Particle Composition Analysis

[11] The composition of individual particles, either ambient or heated residual, was determined using the PALMS instrument. The instrument is described in detail elsewhere [Thomson et al., 2000; Murphy et al., 2006] and a brief description is provided here. Aerosols are brought into the analysis region of the PALMS instrument through an aerodynamic lens system with upstream pressure control in order to focus particles between 0.1 and 2 μm aerodynamic diameter into a narrow beam. The particles pass through two parallel frequency-doubled Nd:YAG laser beams (532 nm) and the transit time between the beams provides a measure of particle aerodynamic diameter (da). Light scattering from the second beam triggers a pulse from an excimer laser (193 nm) that ablates and ionizes the particle. The detection threshold of the scattering signal results in a rapid falloff in the particle detection efficiency below about 0.35 μm. The ions formed in the excimer pulse are detected using a time of flight mass spectrometer. The mass spectrometer records a mass spectrum of either positive or negative ions for a single particle. During the TC4 mission, the instrument was located in the DC-8 cabin. The instrument could operate either fully automated or with manual intervention while on the aircraft, alternating between periods of acquiring positive or negative mass spectra with brief periods of time for laser realignment.

[12] The collected mass spectra were postprocessed to subtract backgrounds, eliminate false triggers, and correct shifted mass spectra. The individual peaks in the mass spectra are expressed as fractions of the total number of ions for a given particle. This is because for similar particles the relative peak sizes have been found to be more consistent than the absolute number of ions formed from the laser pulse. A clustering algorithm based on the relative areas of all peaks within a spectrum has been used to categorize mass spectra from an entire mission into a small number of common particle types to facilitate data analysis [Murphy et al., 2003]. Particles with biomass burning origins are distinguished from other mixed sulfate-organic particles in positive spectra by the presence of a significant nonmineral potassium ion signal at m/z 39 as described in detail by Hudson et al. [2004] Sea salt particles are distinguished by ions such as Na+, Mg+, K+, Cl, and clusters thereof.

[13] Unheated inlet data used for comparison with the heated residuals are limited to those particles sampled within 300 s and 200 m altitude of the nearest heated sampling period. Heated samples that occurred during ascents or descents and therefore did not have unheated comparison samples meeting these criteria were removed from the data set considered in this analysis. During the mission, PALMS usually acquired measurable mass spectra from over 90% of detected particles so there was little systematic bias against sulfate or other particle types merely because they were difficult to ionize.

3. Results and Discussion

3.1. Changes in Observed Size Distributions

[14] Since PALMS measures the aerodynamic diameter along with the composition of individual particles, size distributions for different types of particles can be investigated by aggregating the size data based on particle composition. Figure 2 shows the size distributions measured by PALMS for sea salt particles in the marine boundary layer, sulfate-organic particles in the free troposphere, and biomass burning particles in the boundary layer over the Colombian jungle sampled from both the ambient and heated inlet flows. These histograms represent raw counts of aerodynamic diameter measured by the PALMS instrument and are not corrected for inlet transmission and size-dependent particle detection efficiency.

Figure 2.

Comparison of unheated (black) and heated residual (gray) aerodynamic size distributions for (a) sea salt particles in the marine boundary layer, (b) biomass burning and organic sulfate particles in the free troposphere, and (c) biomass burning and organic sulfate particles in the continental boundary layer over the Colombian jungle. The lower size limit near 0.2 μm is set by the reduced efficiency of sampling and detection of particles smaller than about 0.3 μm diameter by PALMS.

[15] Aerosol particles in the marine boundary layer were almost always either sea salt or particles entrained from the free troposphere. The size distribution of just the sea salt particles measured by PALMS in the marine boundary layer shows a broad peak centered at 1 μm da (Figure 2a). The size distribution does not exhibit any significant changes when the particles are sampled through the heated inlet, indicating that there was not likely a significant loss of mass from the sea salt particles upon heating.

[16] More than 90% of the particles sampled in the free troposphere were sulfate-organic mixtures with or without biomass burning influence. The size distribution of sulfate-organic particles sampled in the free troposphere had a mode aerodynamic diameter around 0.4 μm, but with a small tail out to around 0.9 μm (Figure 2b). The falloff in the size distribution at smaller diameters is due to the decrease in sampling efficiency of the PALMS instrument at diameters below 0.35 μm. The size distribution of the heated residual aerosols with sulfate-organic classification had a similar shape, but is shifted to slightly smaller sizes, with a mode diameter around 0.35 μm and the tail extending to only 0.7 μm. Since this is a change in the aerodynamic diameter, it is not necessarily the case that this represents a change in particle geometric diameter, but could also arise from changes to the particle density or shape.

[17] Particles identified as of biomass burning origin dominated the particle types analyzed in the low-altitude flight segment over the Colombian jungle, accounting for 72% of ambient and 78% of heated residual positive spectra. The size distribution of these particles resembles that of the free tropospheric sulfate-organic particles with a narrowly peaked distribution, but at a slightly smaller mode diameter of 0.35 μm (Figure 2c). The size distribution of the heated residual particles again shows a slight shift to smaller sizes with a mode diameter of 0.3 μm. A second mode in the biomass burning aerosol population is also discernable between 0.8 and 1.4 μm, which becomes more apparent in the heated residual population as these particles are less likely to shrink below the PALMS detection threshold.

3.2. Changes in Particle Sampling Rate

[18] Evaporation in the thermal denuder causes some particles to shrink to sizes with reduced detection efficiency or below the PALMS detection limit altogether. One measure of this is the decrease in the rate at which particles were sampled between the heated and proximate unheated sampling periods. In the marine boundary layer, where a significant fraction of the particles sampled were large sea salt particles, total particle sampling rates through the heated inlet averaged 65% that of the ambient sampling rates. Most of the evaporated particles contributing to the decrease in sampling rate were not sea salt since the fraction of particles identified as sea salt increased from 34% in ambient samples to 73% in heated samples. In the free troposphere, where the ambient particles sampled were dominated by non-biomass-burning sulfate-organic particles (75% of positive spectra), the heated sampling rates averaged only 15% that of the proximate ambient sampling rates, indicating that a significant fraction of the ambient aerosols were evaporated to sizes smaller than the PALMS detection threshold. In the Colombian jungle boundary layer, the heated sampling rate averaged 33% of the ambient sampling rate. The difference between the free troposphere and Colombian jungle heated detection rates indicates that particles of biomass burning origin are less likely to shrink to below the PALMS detection threshold than other sulfate-organic aerosols.

3.3. Sea Salt Particles in the Marine Boundary Layer

[19] A significant fraction of the particles sampled in the marine boundary layer were sea salt particles. Figure 3a shows on a log scale the average negative ion spectrum of sea salt particles sampled in the marine boundary layer through the ambient temperature inlet. The spectrum is dominated by chlorine at m/z 35 and 37 (Cl) and 93 and 95 (NaCl·Cl), oxygen at m/z 16 (O) and 17 (OH), and sulfate at m/z 80 (SO3) and 96 (SO4). There are small peaks attributable to organics at m/z 12 (C), 24 (C2), 25 (C2H), and 26 (C2H2; CN). m/z 46 is NO2, a fragment ion from nitrate. This spectrum is typical of that observed from fresh sea salt particles. Since chloride forms negative ions much more efficiently than organics do, the small carbon-containing peaks indicate that a significant minority of the mass of the sea salt aerosol was organic [Middlebrook et al., 1998].

Figure 3.

Change in sea salt particle negative spectra. (a) Average mass spectrum of unheated sea salt particles in the marine boundary layer, (b) observed average mass spectrum of heated sea salt particles, and (c) difference in the mass spectra.

[20] Figure 3b shows the average spectrum of sea salt particles sampled through the heated inlet. This spectrum is dominated by the same peaks and overall exhibits only small changes from the average ambient sample spectrum. To better discern the effect of heated sampling on the aerosol composition, Figure 3c shows the difference spectrum determined by subtracting the average ambient spectrum from the average heated spectrum. Downward bars represent decreases in relative contribution in the heated spectrum while upward bars denote relative increases. The difference spectrum shows that heating the particles led to a decrease in the relative signals from chlorine and sulfate species on the order of a few percent. The loss of chlorine and sulfate, though small, is interesting since it implies that some of the chlorine and sulfate were present in forms that were volatile at 300°C. Dominant species in sea salt, such as sodium chloride, are not volatile at this temperature [Brooks et al., 2002]. The carbonaceous peaks increased in relative size in the heated samples, indicating that a larger fraction of organic carbon survived the heating than did chlorine. Since only a small fraction of the chlorine was likely to have been volatile, this implies that a large fraction of the organics must have survived the heating.

[21] Negligible differences were observed between the positive spectra of ambient and heated residual sea salt spectra. The dominant positive ions are from nonvolatile species such as Na, Mg, and K.

3.4. Sulfate-Organic Particles in the Free Troposphere

[22] The dominant particle type detected by PALMS above 6000 m altitude during TC4 was a sulfate-organic internal mixture. Figure 4a shows the average negative ion spectrum of sulfate-organic particles sampled through the unheated inlet line during times proximate to heated samples. Biomass burning particles are not distinguished from other sulfate-organic particles in negative ion spectra since the potassium marker is not detected. The largest peaks in the negative spectra of sulfate-organic particles are the sulfate peaks at m/z 80, 81 (HSO3), 96, 97 (HSO4), and 99 (H34SO4), O and OH at m/z 16 and 17, and organics at m/z 12, 24, 25, and 26. The averaged spectrum of sulfate-organic heated residuals (Figure 4b) shows decreases in the sulfate ion signals by more than an order of magnitude and corresponding increases in the organic ion signals. The difference spectrum (Figure 4c) clearly shows the near complete loss of sulfate and increase in the fractional contribution from organic ion signals. Unlike the sea salt spectra above, the oxygen ion signals at m/z 16 and 17 are smaller in the heated sulfate-organic residuals than in the ambient particles.

Figure 4.

Change in sulfate-organic particle negative spectra. (a) Average mass spectrum of unheated sulfate-organic particles sampled in the free troposphere, (b) average mass spectrum of heated sulfate-organic residuals, and (c) difference in the mass spectra.

[23] Based on in-flight comparisons between PALMS and other instruments on earlier missions [Murphy et al., 2006], the relative sulfate and organic mass fractions of these particles can be estimated from the relative intensities of the sulfate and organic negative ion signals. For unheated sulfate-organic aerosols, the average estimated sulfate mass fraction was 0.59 (±0.30), with a relatively flat distribution among individual particles between 0.01 and 0.99. For heated residual particles, the average estimated sulfate mass fraction was 0.002 (±0.002), indicating essentially complete absence of sulfate in the residuals.

[24] Figure 5a shows the averaged positive ion spectrum of sulfate-organic particles in the free troposphere. In this spectrum the sulfate is visible as SO+ (m/z 48), SO2+ and HSO2+ (m/z 64 and 65), HSO3+ (m/z 81), and H2SO4·H+ (m/z 99). The dominant organic peaks are m/z 12 (C+) and 28 (CO+), with additional contributions from m/z 24 (C2+), 26 (C2H2+), and 29 (CHO+). Organic fragments are also observed at many other masses below m/z 50. m/z 30, the second largest peak in the spectrum, is NO+, an ion produced commonly from nitrate, ammonium, and other organic nitrogen species. Figure 5b shows the average spectrum of sulfate-organic heated residuals. The sulfate peaks have vanished (with the exception of a small amount of m/z 48, which can be attributed to C4+) and the organic portion of the spectrum has simplified somewhat with many of the minor peaks decreasing. The m/z 30 peak decreased from 22% of the total ion current in the ambient spectrum to 1% in the heated spectrum, indicating that most of the nitrogen species have also evaporated. The difference spectrum in Figure 5c shows that there were significant increases in the relative signals at m/z 12 and 24 and smaller increases at m/z 25, 26, and 36, while the CO+ peak at m/z 28 decreased.

Figure 5.

Change in sulfate-organic particle positive spectra. (a) Average mass spectrum of unheated sulfate-organic particles sampled in the free troposphere, (b) average mass spectrum of heated sulfate-organic residuals, and (c) difference in the mass spectra.

[25] The fraction of free tropospheric particles categorized as biomass burning increased significantly when sampling through the heated inlet. Approximately 19% of particles were classified as biomass burning in all proximate unheated mass spectra, whereas in the heated samples this increased to 70% of particles. There are three likely contributions to this observed difference. The first is that biomass burning particles in the free troposphere tended to be slightly larger than other sulfate-organic particles (not shown) and the second is that the typically lower sulfate content of biomass burning particles led to smaller decreases in diameter. These two factors both lead to a larger fraction of biomass burning particles remaining within the PALMS detection size range. A third potential cause is that as particles evaporated, the increase in the relative contribution to the total ion current from small amounts of potassium crossed the threshold used to classify particles as of biomass burning origin, leading to a recategorization. Examination of histograms of the potassium peak size shows that this third reason was less important than changes in particle size.

[26] Based on the relative sampling rate between heated and unheated inlets, at least 15% of free tropospheric particles in the PALMS size range left measurable residuals. The mode diameter of the detected residuals decreased by about 10% from the unheated aerosols (see Figure 2). Taken at face value, this would indicate that about 11% of the aerosol mass in the PALMS size range survived heating to 300°C. The actual number of surviving particles was probably much higher than the 15% detected, due to the decreasing detection and transmission efficiency of PALMS between 0.3 and 0.2 μm. For example, a 0.3 μm particle that evaporates down to 0.2 μm is less likely to be detected by up to a factor of 10. Accounting for the decrease in detection efficiency, roughly 20 to 40% of the initially detectable particle mass survived heating. Elemental carbon and potassium in the original biomass burning particles cannot account for this much mass. Single particle soot photometer measurements on a different aircraft but in the same time and vicinity during TC4, showed that elemental carbon comprised less than 2% of the mass of accumulation mode particles in the free troposphere (J. R. Spackman, personal communication, 2009). The complete evaporation of sulfate by itself accounts for a loss of about 55% of the particle mass, so a substantial fraction of the organic mass appears to have survived heating.

[27] The identification of the heated residuals as including a substantial organic carbon mass contribution is further supported by cluster analysis of the mass spectra. Despite some simplification of the mass spectra from many organic peaks toward relatively more C+ and C2+ (Figure 5c), the residual spectra are not the same as those from elemental carbon, which typically contain significant signals from longer carbon chain ions at m/z 48, 60 and 72. None of the heated residual particles were assigned by the cluster analysis to the same category as the soot particles observed in the polluted boundary layer over Costa Rica.

[28] Additional information about the properties of the sulfate-organic heated residual particles can be gained by comparing the YAG laser scattering signals from the heated residuals with those from unheated sulfate-organic aerosol. Figure 6 shows a plot of the YAG scatter signal versus the aerodynamic diameter for heated residuals and unheated sulfate-organic particles with a sulfate fraction less than 5%. The similarity in the observed scatter signals between all heated organic residuals and unheated organic-rich particles of the same aerodynamic diameter indicates that they have similar optical sizes and therefore a similar density to shape factor ratio. If we assume that the shape of the heated residuals has not changed significantly (i.e., become significantly nonspherical), then we can infer that the density of the residual organic material remained similar to that in the unheated aerosols, in the range of 1.0–1.2 based on calibrations with polystyrene latex spheres [Murphy et al., 2004].

Figure 6.

Plot of the YAG scattering height versus aerodynamic diameter for free tropospheric sulfate-organic heated residuals (red) and for unheated sulfate-organic particles with a sulfate mass fraction <0.05 (blue). The large symbols represent the median values within 0.1 μm bins of aerodynamic diameter, and the error bars indicate the upper and lower quartiles. For contrast, the green trace shows the median values and interquartile range for the scattering signal from unheated sulfate-organic particles with a sulfate mass fraction >0.95. Particles with the same aerodynamic diameter but lower densities have larger geometric diameters and hence scatter more light.

3.5. Biomass Burning Particles in the Colombian Jungle Boundary Layer

[29] Heated samples were acquired in the boundary layer over the jungle in Colombia during one flight on 8 August 2006. Despite this being the rainy season, the particle type classification of acquired positive spectra during the low-altitude leg (<600 m) was dominated by biomass burning aerosols (72% of positive mass spectra). The absolute particle concentration was fairly low (optical particle counter concentrations (Dp > 300 nm) of about 30 cm−3), so the biomass burning particles were probably from scattered small fires, not the large-scale burning characteristic of the Amazon during the dry season.

[30] The average positive ion spectrum of ambient temperature biomass burning particles (Figure 7a) is similar to that of the free tropospheric sulfate-organic aerosols shown above (Figure 5a), but the sulfate peaks are substantially smaller relative to the organic peaks and the m/z 39 peak from potassium is the largest peak in the spectrum, contributing 39% on average of the total ion current. Potassium ionizes very easily so this peak can arise from small amounts of potassium in a particle. The ratios of the organic peaks also exhibit significant differences, with the organic signal being much more concentrated at m/z 12 in the biomass burning particles than in the free tropospheric sulfate-organic particles.

Figure 7.

Change in biomass burning particle positive spectra. (a) Average mass spectrum of unheated biomass burning particles sampled over the jungle in Colombia, (b) average mass spectrum of heated biomass burning residuals, and (c) difference in the mass spectra.

[31] The average spectrum of biomass burning heated residuals is shown in Figure 7b. Similar to the sulfate-organic particles in the free troposphere, the sulfate signal has decreased by more than an order of magnitude, indicating nearly complete evaporation of sulfate from the particles. The behavior of the organic peaks, however, is different, with only the signal at m/z 12 increasing in the heated residuals. The fraction of particles classified as biomass burning increased slightly in the heated residuals to 78%. Analysis of the shifts in size and particle sampling rates between the heated and unheated inlets shows that, like the free tropospheric particles, it is difficult to explain the surviving mass without a significant contribution from nonelemental organic carbon in the 300°C residuals.

4. Summary and Implications

[32] The TC4 mission provided the opportunity for the PALMS single particle mass spectrometer to analyze nonvolatile aerosol residuals sampled through a heated inlet and compare them with unheated aerosols to examine the composition of the nonvolatile aerosol component in different environments. For heated sampling aerosols passed through a 300°C section of tubing with a residence time of 0.26 s, which laboratory tests demonstrated to fully evaporate 0.5 μm ammonium sulfate aerosols.

[33] The results showed that, as expected, there were only minor changes to fresh sea salt particle composition, with no significant change in the measured size distribution. Some loss of chlorine and sulfate was observed, on the order of a few percent of the fractional ion signals. The ion signals from carbon associated with sea salt actually increased on a relative basis, indicating that the organic carbon was less volatile than some of the chloride. A significant fraction of organic carbon in sea salt particles has been shown to consist of high molecular weight biological molecules such as lipopolysaccharides [Facchini et al., 2008], compounds that might be expected to pyrolyze rather than evaporate on heating.

[34] For particles that were internal mixtures of organics and sulfate, near quantitative removal of sulfate was observed and the residuals were largely composed of organic and other carbon. The fraction of particles identified as being of biomass burning origin increased after heated sampling, which is likely due to the higher organic mass fraction found in these particles and possibly also the nature of the organics present. This result implies that highly organic aerosols, such as those from biomass burning sources, will preferentially survive thermal denuder heating for subsequent analysis.

[35] The fragmentative nature of the PALMS analysis does not reveal details about possible changes in the species comprising the organic carbon, but does allow it to be distinguished from elemental carbon. Carbon in the heated residues included significant organic as well as elemental carbon content. This is consistent with the analysis of thermograms from airborne filter samples [Novakov et al., 1997] that indicated that carbon evolving at temperatures above 300°C included both organic and elemental carbon. Organic carbon pyrolyzed in an inert atmosphere at lower temperatures requires up to 700°C to be released [Boparai et al., 2008]. The measurements presented here confirm that the survival of substantial amounts of organic carbon at 300°C applies to aerosol particles as well as particles deposited on filters. It also confirms that the presence of organics in single particles after a thermal denuder, as measured by Denkenberger et al. [2007], applies to regions as disparate as the marine boundary layer and the free troposphere as well as the urban area of that study.

[36] Using similar inlet hardware on the DC-8 as the measurements described here but on an earlier mission, Clarke et al. [2007] measured size distributions of particles with and without heating to temperatures up to 400°C. Correlations with black carbon indicated that it could not account for all of the remaining mass. Clarke et al. [2007] therefore attributed much of the heated residual mass to organics, a conclusion supported by our data. On the other hand, the presence of significant quantities of organics that survive heating to 300°C and the ubiquity of organic carbon in atmospheric aerosols means that earlier measurements of size distributions after heating to 150°C [Clarke et al., 1987; Clarke, 1991; Orsini et al., 1999] cannot be simply interpreted in terms of sulfuric acid and ammonium sulfate. The amount of organic material that does not volatilize, or volatilizes slowly, at even higher temperatures has implications for thermal desorption instruments such as the AMS, where only carbon that volatilizes within less than a few seconds at 600°C in bulk aerosol (MS) sampling mode and a few milliseconds in single particle modes is detected [Jayne et al., 2000; Drewnick et al., 2005; Huffman et al., 2009b]. Evidence of slow volatilization of organics in the AMS has recently been reported based on analysis of changes in instrumental background signals [Huffman et al., 2009b].

[37] Most forms of sulfate appear to be quantitatively removed by heating aerosols to 300°C for a fraction of a second, but the response of the organic fraction of aerosols is more complicated. Because some organics survive the heating, it is not possible to interpret the residuals as completely composed of materials such as sea salt in the marine boundary layer or elemental carbon in regions influenced by biomass burning.


[38] We wish to thank the managers and crew of the NASA DC-8 for their support and accommodation during the TC4 mission. This work was supported by NOAA Climate and Global Change Program funding and by a grant from the NASA Science Mission Directorate.