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Thermal-optical evolved gas analysis (TOEGA) is a conventional method for classifying carbonaceous aerosols as organic carbon (OC) and elemental carbon (EC). Its main source of uncertainty arises from accounting for pyrolized OC (char), which has similar behavior to the EC originally present on the filter. Sample composition can also cause error, at least partly by complicating the charred carbon correction. In this study, lab generated metal salt particles, including alkali (NaCl, KCl, Na<sub>2</sub>SO<sub>4</sub>), alkaline-earth (MgCl<sub>2</sub>, CaCl<sub>2</sub>) and transition metal salts (CuCl<sub>2</sub>, FeCl<sub>2</sub>, FeCl<sub>3</sub>, CuCl, ZnCl<sub>2</sub>, MnCl<sub>2</sub>, CuSO<sub>4</sub>, Fe<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>), were deposited on a layer of diesel particles to investigate their effect on EC and OC quantification with TOEGA. Measurements show that metals reduce the oxidation temperature of EC and enhance the charring of OC. The split point used to determine classification of EC vs. OC is more dependent on changes in EC oxidation temperature than it is on charring. The resulting EC/OC ratio is reduced by 0–80% in the presence of most of the salts, although some metal salts increase reported EC/OC at low metal to carbon ratios. The results imply that EC/OC ratios of ambient aerosols quantified with TOEGA have variable low biases due to the presence of metals. In general, transition metals are more active than alkali and alkaline-earth metals; copper is the most active. Copper and iron chlorides are more active than sulfates. The melting point of metal salts is strongly correlated with the increase of OC charring, but not with the reduction of EC oxidation temperature. Other chemistry, such as redox reactions, may affect the EC oxidation. A brief discussion of possible catalytic mechanisms for the metals is provided.
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Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23–0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.21 to 0.37.
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Aerosol mass spectrometry has proved to be a powerful tool to measure submicron particulate composition with high time resolution. Factor analysis of mass spectra (MS) collected worldwide by aerosol mass spectrometer (AMS) demonstrates that submicron organic aerosol (OA) is usually composed of several major components, such as oxygenated (OOA), hydrocarbon-like (HOA), biomass burning (BBOA), and other primary OA. In order to help interpretation of component MS from factor analysis of ambient OA datasets, AMS measurements of different primary sources is required for comparison. Such work, however, has been very scarce in the literature, especially for high resolution MS (HR-MS) measurements, which performs improved characterization by separating the ions of different elemental composition at each <i>m</i>/<i>z</i> in comparison with unit mass resolution MS (UMR-MS) measurements. In this study, primary emissions from four types of Chinese cooking (CC) and six types of biomass burning (BB) were simulated systematically and measured using an Aerodyne High-Resolution Time-of-Flight AMS (HR-ToF-AMS). The MS of the CC emissions show high similarity, with <i>m</i>/<i>z</i> 41 and <i>m</i>/<i>z</i> 55 being the highest signals; the MS of the BB emissions also show high similarity, with <i>m</i>/<i>z</i> 29 and <i>m</i>/<i>z</i> 43 being the highest signals. The MS difference between the CC and BB emissions is much bigger than that between different CC (or BB) types, especially for the HR-MS. The O/C ratio of OA ranges from 0.08 to 0.13 for the CC emissions and from 0.18 to 0.26 for the BB emissions. The UMR ions of <i>m</i>/<i>z</i> 43, <i>m</i>/<i>z</i> 44, <i>m</i>/<i>z</i> 57, and <i>m</i>/<i>z</i> 60, usually used as tracers in AMS measurements, were examined for their HR-MS characteristics in the CC and BB emissions. In addition, the MS of the CC and BB emissions are also compared with component MS from factor analysis of ambient OA datasets observed in China, as well as with other AMS measurements of primary sources in the literature. The MS signatures of cooking and biomass burning emissions revealed in this study can be used as important reference for factor analysis of ambient OA datasets, especially for the relevant studies in East Asia.
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Observational results of diurnal variations of humidity from Odin-SMR and AURA-MLS, and cloud ice mass from Odin-SMR and CloudSat are presented for the first time. Comparisons show that the retrievals of humidity and cloud ice from these two satellite combinations are in good agreement. The retrieved data are combined from four almost evenly distributed times of the day allowing mean values, amplitudes and phases of the diurnal variations around 200 hpa to be estimated. This analysis is applied to six climatologically distinct regions, five located in the tropics and one over the subtropical northern Pacific Ocean. The strongest diurnal cycles are found over tropical land regions, where the amplitude is ~7 RHi for humidity and ~50% for ice mass. The greatest ice mass for these regions is found during the afternoon, and the humidity maximum is observed to lag this peak by ~6 h. Over tropical ocean regions the variations are smaller and the maxima in both ice mass and humidity are found during the early morning. Observed results are compared with output from three climate models (ECHAM, EC-EARTH and CAM3). Direct measurement-model comparisons were not possible because the measured and modelled cloud ice masses represent different quantities. To make a meaningful comparison, the amount of snow had to be estimated from diagnostic parameters of the models. There is a high probability that the models underestimate the average ice mass (outside the 1-σ uncertainty). The models also show clear deficiencies when it comes to amplitude and phase of the regional variations, but to varying degrees.
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High frequency of agricultural fires is observed every year during the summer months over SW Russia and Eastern Europe. This study investigates the initial injection height of aerosol generated by the fires over these regions during the biomass burning season, which determines the potential for long-range transport of the smoke. This information is critical for aerosol transport modeling, as it determines the smoke plume evolution. The study focuses on the period 2006–2008, and is based on observations made by the CALIOP instrument on board the NASA CALIPSO satellite. MODIS data are synergistically used for the detection of the fires and the characterization of their intensity. CALIPSO aerosol vertical distributions generated by the active fires are analyzed to investigate the aerosol top height which is considered dependent on the heat generated by the fires and can be associated with the initial injection height. Aerosol top heights of the vertically homogenous smoke layers are found to range between 1.6 and 5.9 km. Smoke injection heights from CALIPSO are compared with mixing layer heights taken by the European Centre for Medium-range Weather Forecast (ECMWF), to investigate the direct injection of smoke particles into the free troposphere. Our results indicate that the aerosol plumes are observed within the boundary layer for the 50% of the cases examined. For the rest of the cases, the strong updrafts generated by the fires resulted to smoke injection heights greater than the ECMWF estimated mixing layer by 0.5 to 3.0 km, indicating a direct smoke injection into the free troposphere. The smoke injection height showed a dependence on the MODIS-Land Fire Radiative Power product which is indicative of the fire intensity, especially in the cases of lower static stability in the upper part of the boundary layer and the free troposphere.
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We report the first hourly in-situ measurements of speciated organic aerosol (OA) composition in an urban environment. Field measurements were made in southern California at the University of California–Riverside during the 2005 Study of Organic Aerosol at Riverside (SOAR), which included two separate measurement periods: a summer study (15 July–15 August) and a fall study (31 October–28 November). Hourly measurements of over 300 semivolatile and nonvolatile organic compounds were made using the thermal desorption aerosol gas chromatograph (TAG). Positive matrix factorization (PMF) was performed on a subset of these compounds to identify major components contributing to submicron (i.e., PM<sub>1</sub>) OA at the site, as measured by an aerosol mass spectrometer (AMS). PMF analysis was performed on an 11-day focus period in each season, representing average seasonal conditions during the summer and a period of urban influence during the fall. As a result of this analysis, we identify multiple types of primary and secondary OA (POA and SOA). Secondary sources contribute substantially to fine OA mass at Riverside, which commonly receives regional air masses that pass through metropolitan Los Angeles during the summer. Four individual summertime SOA components are defined, and when combined, they are estimated to contribute an average 88% of the total fine OA mass during summer afternoons according to PMF results. These sources appear to be mostly from the oxidation of anthropogenic precursor gases, with one SOA component having contributions from oxygenated biogenics. During the fall, three out of four aerosol components that contain SOA are inseparable from covarying primary emissions, and therefore we cannot estimate the fraction of total OA that is secondary in nature during the fall study. Identified primary OA components are attributed to vehicle emissions, food cooking, primary biogenics, and biomass burning aerosol. While a distinction between local and regional vehicle emissions is made, a combination of these two factors accounted for approximately 11% of observed submicron OA during both sampling periods. Food cooking operations contributed ~10% of submicron OA mass during the summer, but was not separable from SOA during the fall due to high covariance of sources. Biomass burning aerosol contributed a larger fraction of fine OA mass during the fall (~11%) than compared to summer (~7%). Primary biogenic aerosol was also identified during the summer, contributing ~1% of the OA, but not during the fall. While the contribution of both local and regional primary vehicle OA accounts for only ~11% of total OA during both seasons, gas-phase vehicle emissions likely create a substantial fraction of the observed SOA as a result of atmospheric processing.
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Using one month of the cloud-resolving Nonhydrostatic Icosahedral Atmospheric Model (NICAM) simulations, we examined the impact of different definitions of clear-sky flux on the determination of longwave cloud radiative forcing (CRF). Because the satellite-like cloud-free composite preferentially samples drier conditions relative to the all-sky mean state, the conventional clear-sky flux calculation using the all-sky mean state in the model may represent a more humid atmospheric state in comparison to the cloud-free state. The drier bias is evident for the cloud-free composite in the NICAM simulations, causing an overestimation of the longwave CRF by about 10% compared to the NICAM simulated longwave CRF. Overall, water vapor contributions of up to 10% of the total longwave CRF should be taken account for making model-generated cloud forcing comparable to the satellite measurements.
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In the Arctic winter 2003, in-situ measurements of the long-lived trace gases N<sub>2</sub>O, CFC-11 (CCl<sub>3</sub>F), H-1211 (CBrClF<sub>2</sub>), CH<sub>4</sub>, O<sub>3</sub> and H<sub>2</sub>O have been performed on board the high-altitude aircraft M55 Geophysica. The data are presented and used to study transport into the lowermost stratosphere (LMS). The LMS can be regarded as a mixture of fractions of air originating in (i) the troposphere, (ii) the extra-vortex stratosphere above 400 K and (iii) the Arctic vortex above 400 K. These fractions are determined using a simple mass balance calculation. The analysis exhibits a strong tropospheric influence of 50% ± 15% or more in the lowest 20 K of the high-latitude LMS. Above this region the LMS is dominated by air masses having descended from above 400 K. Below the Arctic vortex region at potential temperatures above 360 K, air in the LMS is a mixture of extra-vortex stratospheric and vortex air masses. The vortex fraction increases from about 40% ± 15% at 360 K to 100% at 400 K for equivalent latitudes >70° N. This influence of air masses descending through the bottom of the polar vortex increases over the course of the winter. By the end of winter a significant fraction of 30% ± 10% vortex air in the LMS is found even at an equivalent latitude of 40° N. Since the chemical and dynamical history of vortex air is distinct from that of mid-latitude stratospheric air masses, this study implies that the composition of the mid- to high-latitude LMS during late winter and spring is significantly influenced by the Arctic vortex.
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Aerosol particle number size distribution and chemical composition were measured at two low altitude sites, one urban and one relatively pristine valley, in Central Nepal during the 2009 pre-monsoon season (May–June). This is the first time that aerosol size distribution and chemical composition were measured simultaneously at lower elevations in the middle Himalayan region in Nepal. The aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS, 14–340 nm), and the chemical composition of the filter samples collected during the field campaign was analyzed in the laboratory. Teflon membrane filters were used for ion chromatography (IC) and water-soluble organic carbon and nitrogen analysis. Quartz fiber filters were used for organic carbon and elemental carbon analysis. Multi-lognormal fits to the measured aerosol size distribution indicated a consistent larger mode around 100 nm which is usually the oldest, most processed background aerosol. The smaller mode was located around 20 nm, which is indicative of fresh but not necessarily local aerosol. The diurnal cycle of the aerosol number concentration showed the presence of two peaks (early morning and evening), during the transitional periods of boundary layer growth and collapse. The increase in number concentration during the peak periods was observed for the entire size distribution. Although the possible contribution of local emissions in size ranges similar to the larger mode cannot be completely ruled out, another plausible explanation is the mixing of aged elevated aerosol in the residual layer during the morning period as suggested by previous studies. Similarly, the evening time concentration peaks when the boundary layer becomes shallow concurrent with increase in local activity. A decrease in aerosol number concentration was observed during the nighttime with the development of cold (downslope) mountain winds that force the low level warmer air in the valley to rise. The mountain valley wind mechanisms induced by the topography along with the valley geometry appear to have a strong control in the diurnal cycle of the aerosol size distribution. During the sampling period, the chemical composition of PM<sub>2.5</sub> was dominated by organic matter at both sites. Organic carbon (OC) comprised the major fraction (64–68%) of the aerosol concentration followed by ionic species (24–26%, mainly SO<sub>4</sub><sup>2−</sup> and NH<sub>4</sub><sup>+</sup>). Elemental Carbon (EC) compromised 7–10% of the total composition and 27% of OC was found to be water soluble at both sites. The day-to-day variability observed in the time series of aerosol composition could be explained by the synoptic scale haze that extended to the sampling region from the Indian Gangetic Plain (IGP), and rainfall occurrence. In the presence of regional scale haze during dry periods, the mean volume aerosol concentration was found to increase and so did the aerosol mass concentrations.
