Observations of Nocturnal Sulfuric Acid Formation in Pittsburgh, PA.

Abstract. Sulphuric acid concentrations were measured and calculated based on pseudo steady state model with corresponding measurements of CO, NOx, O3, SO2, methane and non-methane hydrocarbon (NMHC) concentrations as well as solar spectral irradiance and particle number concentrations with size distributions. The measurements were performed as a part of the EU project QUEST (Quantification of Aerosol Nucleation in the European Boundary layer) during an intensive field campaign, which was conducted in Hyytiälä, Finland in March–April 2003. In this paper, the closure between measured and calculated H2SO4 concentrations is investigated. Besides that, also the contribution of sulphuric acid to nucleation mode particle growth rates is studied. Hydroxyl and hydroperoxy radical concentrations were determined using a pseudo steady state box model including photo stationary states. The maximum midday OH concentrations ranged between 4.1×105 to 1.8×106 molecules cm-3 and the corresponding values for HO2 were 1.0×107 to 1.5×108 molecules cm-3. The dominant source term for hydroxyl radicals is the reaction of NO with HO2 (56%) and the reaction of CO with OH covers around 41% of the sinks. The sulphuric acid source term is the reaction SO2 with OH and the sink term is condensation of sulphuric acid. The closure between measured and calculated sulphuric acid concentrations is achieved with a high agreement to the measured values. In sensitivity studies, we used different values for the non-methane hydrocarbons, the peroxy radicals and nitrogen dioxide. The best fits between calculated and measured values were found by decreasing the NO2 concentration when it exceeded values of 1.5 ppb and doubling the non-methane hydrocarbon concentrations. The ratio, standard deviation and correlation coefficient between measured and calculated sulphuric acid concentrations are 0.99, 0.412 and 0.645, respectively. The maximum midday sulphuric acid concentrations varied between 3×105 to 1.9×107 molecules cm-3 for the measurements and 3×105 to 1.4×107 molecules cm-3 for the calculations, respectively. An average participation of sulphuric acid to the nucleation mode particle growth rates is 8.8%. Classifying the days into two groups – ''polluted'' days with air masses originated over Central Europe or UK, and ''cleaner'' days with air masses originated over the Northern Atlantic or the Polar regions – reflects an equal sulphuric acid contribution to the aerosol growth in both air mass classes.

Abstract. Over the Indian region, aerosol absorption is considered to have a potential impact on the regional climate, monsoon and hydrological cycle. Black carbon (BC) is the dominant absorbing aerosol, whose absorption potential is determined mainly by its microphysical properties, including its concentration, size and mixing state with other aerosol components. The Indo-Gangetic Plain (IGP) is one of the regional aerosol hot spots with diverse sources, both natural and anthropogenic, but still the information on the mixing state of the IGP aerosols, especially BC, is limited and a significant source of uncertainty in understanding their climatic implications. In this context, we present the results from intensive measurements of refractory BC (rBC) carried out over Bhubaneswar, an urban site in the eastern coast of India, which experiences contrasting air masses (the IGP outflow or coastal/marine air masses) in different seasons. This study helps to elucidate the microphysical characteristics of BC over this region and delineates the IGP outflow from the other air masses. The observations were carried out as part of South West Asian Aerosol Monsoon Interactions (SWAAMI) collaborative field experiment during July 2016–May 2017, using a single-particle soot photometer (SP2) that uses a laser-induced incandescence technique to measure the mass and mixing state of individual BC particles and an aerosol chemical speciation monitor (ACSM) to infer the possible coating material. Results highlighted the distinctiveness in aerosol microphysical properties in the IGP air masses. BC mass concentration was highest during winter (December–February) (∼1.94±1.58 µg m−3), when the prevailing air masses were mostly of IGP origin, followed by post-monsoon (October–November) (mean ∼1.34±1.40 µg m−3). The mass median diameter (MMD) of the BC mass size distributions was in the range 0.190–0.195 µm, suggesting mixed sources of BC, and, further, higher values (∼ 1.3–1.8) of bulk relative coating thickness (RCT) (ratio of optical and core diameters) were seen, indicating a significant fraction of highly coated BC aerosols in the IGP outflow. During the pre-monsoon (March–May), when marine/coastal air masses prevailed, BC mass concentration was lowest (∼0.82±0.84 µg m−3), and larger BC cores (MMD > 0.210 µm) were seen, suggesting distinct source processes, while RCT was ∼ 1.2–1.3, which may translate into higher extent of absolute coating on BC cores, which may have crucial regional climate implications. During the summer monsoon (July–September), BC size distributions were dominated by smaller cores (MMD ≤ 0.185 µm), with the lowest coating indicating fresher BC, likely from fossil fuel sources. A clear diurnal variation pattern of BC and RCT was noticed in all the seasons, and daytime peak in RCT suggested enhanced coating on BC due to the condensable coating material originating from photochemistry. Examination of submicrometre aerosol chemical composition highlighted that the IGP outflow was dominated by organics (47 %–49 %), and marine/coastal air masses contained higher amounts of sulfate (41 %–47 %), while ammonium and nitrate were seen in minor amounts, with significant concentrations only during the IGP air mass periods. The diurnal pattern of sulfate resembled that of the RCT of rBC particles, whereas organic mass showed a pattern similar to that of the rBC mass concentration. Seasonally, the coating on BC showed a negative association with the mass concentration of sulfate during the pre-monsoon season and with organics during the post-monsoon season. These are the first experimental data on the mixing state of BC from a long time series over the Indian region and include new information on black carbon in the IGP outflow region. These data help in improving the understanding of regional BC microphysical characteristics and their climate implications.

Abstract. Both the size and mixing state of black carbon (BC)-containing aerosols are crucial in estimating the environmental, health and climate impacts of BC. Traffic emissions are a major global source of BC; however, parameterization of BC mass size distributions and mixing states associated with traffic remains lacking due to its dependence on vehicle types and driving conditions. To investigate BC mass size distributions and mixing states associated with traffic emissions, a field campaign was conducted in the Guangzhou urban area during winter, which used a system coupling a differential mobility analyzer (DMA) and a single-particle soot photometer (SP2) to measure BC mass size distributions in the range of 100 to 700 nm. The resolved primary organic aerosols were hydrocarbon-like organic aerosols (HOA) and cooking-like organic aerosols (COA), as well as refractory BC (rBC), which was detected by the DMA–SP2 and correlated highly with HOA (R2=0.88), confirming that traffic emissions are the dominant source of atmospheric BC during the observations. The BC mass size distribution was found to be best fitted by a lognormal distribution, with a geometric mean (Dg,BC) of 258±16 nm, varying between 200 and 300 nm. During daytime, active formation of secondary nitrate and organic aerosols was observed, but it had little effect on the variations of BC mass size distributions. Further analyses revealed that Dg,BC was moderately correlated with rBC / HOA (R2=0.41) in a linear form of Dg,BC=34×rBC/HOA+177, demonstrating that the BC content of traffic emissions significantly impacts the BC mass size distributions. In addition, the size-dependent fractions of BC-containing aerosols in all types of aerosols (fBCc) and the fraction of identified externally mixed (bare/thinly coated) BC particles in all BC-containing aerosols (fext) were also characterized. It was found that the daytime secondary aerosol formation reduced both fBCc and fext, with the decrease in fext being more pronounced for larger particles, possibly due to the higher relative coating thickness. Variations in fext during nighttime were mainly controlled by the emission conditions. For example, fext for 600 nm particles decreased from 0.82 to 0.46 as rBC / HOA increased from 1 to 3.5, while the mass ratios of secondary aerosols to rBC varied little, demonstrating that the BC content also significantly affects the mixing states of freshly emitted BC from traffic emissions. This study suggests that BC content can be used as the key factor to parameterize both the BC mass size distribution and mixing states from traffic emissions, which warrants future comprehensive investigation. In addition, other sources such as biomass burning and coal combustion also contribute substantially to BC emissions, and it was important to investigate whether BC content of other major BC sources than traffic is also important in determining BC mass size distributions and mixing states. Overall, results of this study have significant implications for accurate representation of BC from different sources when modeling the impacts of BC.

<strong class="journal-contentHeaderColor">Abstract.</strong> Soot, or black carbon (BC), aerosol is a major climate forcer with severe health effects. The impacts depend strongly on particle number concentration, size and mixing state. This work reports on two field campaigns at nearby urban and rural sites, 65 km apart, in southern Sweden during late summer 2018. BC was measured using a single particle soot photometer (SP2) and Aethalometers (AE33). Differences in BC concentrations between the sites are driven primarily by local traffic emissions. Equivalent and refractory BC mass concentrations at the urban site were on average a factor 2.2 and 2.5 higher than at the rural site. Peaks in rush hour BC mass concentrations at the urban site were up to a factor ~4 higher than the background levels. The number fraction of particles containing a soot core was significantly higher in the city. BC particles at the urban site were on average smaller by mass and had less coating owing to fresh traffic emissions. The organic components of the fresh plumes were similar in mass spectral signature to &ldquo;hydrocarbon-like organic aerosol&rdquo; (HOA), commonly associated with traffic. Despite the intense local traffic (~30 000 vehicles passing per day), PM1, including organic aerosol, was dominated by aged continental air masses even at the curbside site. The fraction of thickly coated particles at the urban site was highly correlated with the mass concentrations of all measured chemical species of PM1, consistent with aged, internally mixed aerosol. Trajectory analysis for the whole year showed that air masses arriving at the rural site from eastern Europe contained approximately double the amount of BC compared to air masses from western Europe. Furthermore, BC from the largest region emissions in the Malm&ouml;/Copenhagen urban area transported to the rural site is discernable above background levels only when precipitation events are excluded.

<strong class="journal-contentHeaderColor">Abstract.</strong> Soot, or black carbon (BC), aerosol is a major climate forcer with severe health effects. The impacts depend strongly on particle number concentration, size and mixing state. This work reports on two field campaigns at nearby urban and rural sites, 65 km apart, in southern Sweden during late summer 2018. BC was measured using a single-particle soot photometer (SP2) and Aethalometers (AE33). Differences in BC concentrations between the sites are driven primarily by local traffic emissions. Equivalent and refractory BC mass concentrations at the urban site were on average a factor 2.2 and 2.5, with peaks during rush hour up to a factor <span class="inline-formula">∼4</span>, higher than the rural background levels. The number fraction of particles containing a soot core was significantly higher in the city. BC particles at the urban site were on average smaller by mass and had less coating owing to fresh traffic emissions. The organic components of the fresh traffic plumes were similar in mass spectral signature to hydrocarbon-like organic aerosol (HOA), commonly associated with traffic. Despite the intense local traffic (<span class="inline-formula">∼</span> 30 000 vehicles passing per day), PM<span class="inline-formula">₁</span>, including organic aerosol, was dominated by aged continental air masses even at the curbside site. The fraction of thickly coated particles at the urban site was highly correlated with the mass concentrations of all measured chemical species of PM<span class="inline-formula">₁</span>, consistent with aged, internally mixed aerosol. Trajectory analysis for the whole year showed that air masses arriving at the rural site from eastern Europe contained approximately double the amount of BC compared to air masses from western Europe. Furthermore, the largest regional emissions of BC transported to the rural site, from the Malmö–Copenhagen urban area, are discernible above background levels only when precipitation events are excluded. We show that continental Europe and not the Malmö–Copenhagen region is the major contributor to the background BC mass concentrations in southern Sweden.

Soot, or black carbon (BC), aerosol is a major climate forcer with severe health effects. The impacts depend strongly on particle number concentration, size and mixing state. This work reports on two field campaigns at nearby urban and rural sites, 65 km apart, in southern Sweden during late summer 2018. BC was measured using a single particle soot photometer (SP2) and Aethalometers (AE33). Differences in BC concentrations between the sites are driven primarily by local traffic emissions. Equivalent and refractory BC mass concentrations at the urban site were on average a factor 2.2 and 2.5 higher than at the rural site. Peaks in rush hour BC mass concentrations at the urban site were up to a factor ~4 higher than the background levels. The number fraction of particles containing a soot core was significantly higher in the city. BC particles at the urban site were on average smaller by mass and had less coating owing to fresh traffic emissions. The organic components of the fresh plumes were similar in mass spectral signature to “hydrocarbon-like organic aerosol” (HOA), commonly associated with traffic. Despite the intense local traffic (~30 000 vehicles passing per day), PM1, including organic aerosol, was dominated by aged continental air masses even at the curbside site. The fraction of thickly coated particles at the urban site was highly correlated with the mass concentrations of all measured chemical species of PM1, consistent with aged, internally mixed aerosol. Trajectory analysis for the whole year showed that air masses arriving at the rural site from eastern Europe contained approximately double the amount of BC compared to air masses from western Europe. Furthermore, BC from the largest region emissions in the Malmö/Copenhagen urban area transported to the rural site is discernable above background levels only when precipitation events are excluded.

Understanding the OH and peroxy radical chemistry in different environments is essential to predict atmospheric lifetimes and chemical transformations of compounds emitted to the atmosphere of both biogenic and anthropogenic origin. &amp;#160;The extent to which insight into radical chemistry can be gained by comparing simulated and measured radical concentrations has been found to depend on the environment. In particular, significant discrepancies between modeled and measured OH and peroxy radical concentrations have been observed in forested regions characterized by relatively high VOCs and low NO concentrations. The objective of this study was to assess the importance of different radical production and loss processes as well as the role of OH in the production of sulfuric acid, a major precursor of newly formed atmospheric particles, in a sub-urban temperate forest.Measurements were performed as part of the ACROSS project (Atmospheric ChemistRy Of the Suburban foreSt) during June-July of 2022 at a forested site in Rambouillet located along the path of pollution plumes from Paris. OH radicals were measured in a forest clearing at ground-level (about 6 m). Co-located measurements of HO2+RO2 (i.e. the sum of hydroperoxy and organic peroxy radicals) and gas-phase H2SO4 were also made on top of a 40 m tower (~20 m above the forest canopy). &amp;#160;A budget analysis was performed using steady-state calculations for OH and H2SO4 using other available measurements on the ground and on the tower (photolysis rates, NOx, O3, VOCs, OH reactivity, aerosol particle size distribution, etc.). A detailed budget analysis for OH and peroxy radicals was performed with a box-model using a MCM derived mechanism.&amp;#160;Calculated daytime and nighttime OH concentrations on the ground, using measured OH reactivity, showed good correlation with the measurements and reproduced the observed daytime maximum and nighttime levels of about 4&amp;#215;106 molecule cm-3 and (2-6)&amp;#215;105 molecule cm-3, respectively. The production of OH radicals in the clearing and above the canopy during the day was found to be dominated by its regeneration in reactions of HO2 and RO2 with nitric oxide. During the night, the ozonolysis of monoterpenes was a significant OH production pathway with its contribution depending on the nighttime NO concentrations. The box-model resulted in significant underestimation, up to a factor of two in daytime OH and an overestimation of OH reactivity. At the same time, the model sum of peroxy radicals was larger than measurements, especially during the night with lowest observed NO concentration. However, most of the time the model reproduced the observed peroxy radical temporal behavior on the ground and above the canopy, as well as their slightly lower concentrations over the canopy during the day.The formation of H2SO4 was observed every day during the measurement period, with the median maximum H2SO4 concentration of 2.5&amp;#215;106 molecule cm-3 similar to that observed at some other forested sites. The calculated and measured daytime H2SO4 concentrations were highly correlated with formation of sulfuric acid via SO2+OH reaction accounting for (90&amp;#177;20)% of the observed H2SO4.

Cloud condensation nuclei (CCN) activation of black carbon (BC) particles coated with different amounts of inorganic (sulfuric acid) and organic (levoglucosan or succinic acid) compounds was investigated. An evaporation-condensation method was used to produce coated BC particles, and the volume fractions of coating species were measured using the tandem differential mobility analyzer method. Furthermore, the CCN activation of the coated BC particles was measured using a differential mobility analyzer-CCN counter method. Coating with both aforementioned compounds engendered the activation of the BC particles as CCN at a supersaturation of 0.5%. Sulfuric acid coating was associated with the highest CCN activation fraction (= CCN/condensation nuclei), followed by levoglucosan coating and then succinic acid coating; this indicates that the water solubility of the coating compounds played a crucial role in the CCN activation of the coated BC particles. In general, the CCN activation fraction of the coated BC particles increased with the volume fraction of the coating species, but the manner of increase differed with the coating compounds and generation method. A premixed solution method was also used to produce mixed BC particles, and among the coating compounds, sulfuric acid was associated with the highest CCN activation fraction. For a given volume fraction, sulfuric-acid-coated BC particles produced using the premixed solution method showed a higher CCN activation fraction compared with those obtained using the evaporation-condensation method, and this was due to the presence of residual water in the sulfuric-acid-coated BC particles produced using the premixed solution method.

<strong class="journal-contentHeaderColor">Abstract.</strong> Satellite retrievals of tropospheric column formaldehyde (HCHO) and nitrogen dioxide (NO₂) are frequently used to investigate the sensitivity of ozone (O₃) production to concentrations and emissions of nitrogen oxides (NO_x) and volatile organic carbon compounds (VOCs). Space-based remote-sensing information of chemical proxies for NO_x (i.e., NO₂) and VOCs (i.e., HCHO), in particular the ratios of tropospheric column HCHO and NO₂ (FNRs), provide insight into the non-linear relationship of O₃ formation in the lower troposphere. Ultraviolet&ndash;visible (UV/VIS) satellite spectrometers such as the Ozone Monitoring Instrument (OMI) and TROPOspheric Monitoring Instrument (TROPOMI) are capable of providing FNR information with high spatiotemporal coverage, yet a recent study suggested that the biases and noise of satellite retrievals are the largest source of uncertainty for applying satellite-derived FNRs to better understand O₃ production sensitivities. To quantify, and inter-compare, the uncertainties in two of the most commonly-applied satellite sensors to investigate O₃ production sensitivities, we evaluated OMI and TROPOMI retrievals of NO₂ and HCHO tropospheric columns, and resulting FNRs, using Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) and GEO-CAPE Airborne Simulator (GCAS) airborne remote-sensing data taken during the Long Island Sound Tropospheric Ozone Study 2018 (LISTOS 2018). Compared to suborbital remote-sensing observations of tropospheric column NO₂ and HCHO, the accuracy of OMI (using both the National Aeronautics and Space Administration (NASA) version 4 and the Quality Assurance for Essential Climate Variables (QA4ECV) retrieval algorithms) and TROPOMI were magnitude-dependent with high biases (i.e., satellite tropospheric columns &gt; suborbital tropospheric columns) in clean/background environments and a tendency towards a low bias (i.e., satellite tropospheric columns &lt; suborbital tropospheric columns) in moderate to polluted regions. Campaign-averaged NO₂ median biases for OMI, using both the NASA and QA4ECV algorithms, were similar at 0.4&plusmn;4.1 &times; 10¹⁵ molecules cm^-2 (6.3 %) and 0.4&plusmn;4.5 &times; 10¹⁵ molecules cm^-2 (6.8 %), respectively. TROPOMI retrievals of NO₂ had a campaign-averaged median bias of -0.3&plusmn;3.7 &times; 10¹⁵ molecules cm^-2 (-4.8 %) and 0.3&plusmn;3.3 &times; 10¹⁵ molecules cm^-2 (5.8 %) when averaged at finer (0.05&deg; &times; 0.05&deg;) and coarser (0.15&deg; &times; 0.15&deg;) spatial resolution. The three satellite products (NASA OMI, QA4ECV OMI, and TROPOMI) differed more when evaluating tropospheric column HCHO retrievals. Noise in the HCHO retrievals, likely due to low signal-to-noise ratios and the fact the UV/VIS measurement sensitivity at shorter wavelengths used in HCHO retrievals are low in the troposphere, resulted in low correlations and high oscillation/variability in bias (bias standard deviation) in all three satellite products, with campaign-averaged median biases of 5.1&plusmn;7.8 &times; 10¹⁵ molecules cm^-2 (38.7 %), 2.3&plusmn;8.9 &times; 10¹⁵ molecules cm^-2 (17.3 %), 1.9&plusmn;6.7 &times; 10¹⁵ molecules cm^-2 (12.9 %), and 2.9&plusmn;4.9 &times; 10¹⁵ molecules cm^-2 (23.1 %) for NASA OMI, QA4ECV OMI, and TROPOMI at finer and coarser spatial resolution, respectively. Spatially-averaging TROPOMI tropospheric column HCHO, along with NO₂ and FNRs, to coarser resolutions similar to OMI native pixel size proved to reduce the bias standard deviation of the retrieval data. While large median biases, and enhanced variability in bias, were derived for HCHO, errors in both NO₂ and HCHO tropospheric columns tended to offset as all three satellite products compared well to observed FNRs with campaign-averaged median biases from NASA OMI, QA4ECV OMI, and TROPOMI of 0.4&plusmn;3.8 (11.0 %), -0.2&plusmn;3.3 (-5.4 %), and 0.4&plusmn;2.3 (13.0 %), respectively. While satellite-derived FNRs had minimal campaign-averaged median biases, the statistical analysis shows that all satellite FNR values still had large bias standard deviation due to unresolved errors in satellite retrievals of HCHO. This result is important as accurate retrievals (minimal median biases) of FNRs from satellites do not suggest the accuracy of the underlying proxy species. The reduction in noise in satellite retrievals of HCHO with additional calibration and improved sensor design and/or improved a priori information of the vertical profiles of HCHO in the troposphere to avoid the impact of the low measurement sensitivity in the shorter UV/VIS wavelengths used to retrieve HCHO is critical for reducing unresolved biases in satellite retrievals of FNRs. Furthermore, this work demonstrates the large impact of a) a priori vertical profiles of NO₂ and HCHO for calculations of Air Mass Factors in tropospheric column trace gas retrievals in both OMI and TROPOMI, b) spatiotemporal averaging to increase signal-to-noise, and c) different retrieval algorithms on retrieval errors. Finally, the novel diurnal information of tropospheric FNRs that is expected to be provided by the upcoming NASA geostationary sensor Tropospheric Emissions: Monitoring of Pollution (TEMPO) is investigated and compared to low earth orbiting sensors currently applied to investigate tropospheric FNRs.

Household coal combustion is considered as the greatest emission source for black carbon (BC) and an important source for organic carbon (OC) in China. However, measurements on BC and OC emission factors (EF(BC) and EF(OC)) are still scarce, which result in large uncertainties in emission estimates. In this study, a detailed data set of EF(BC) and EF(OC) for household coal burning was presented on the basis of 38 coal/stove combination experiments. These experiments included 13 coals with a wide coverage of geological maturity which were tested in honeycomb-coal-briquette and raw-coal-chunk forms in three typical coal stoves. Averaged values of EF(BC) are 0.004 and 0.007 g/kg for anthracite in briquette and chunk forms and 0.09 and 3.05 g/kg for bituminous coal, respectively; EF(OC) are 0.06 and 0.10 g/kg for anthracite and 3.74 and 5.50 g/kg for bituminous coal in both forms, respectively. Coal maturity was found to be the most important influencing factor relative to coal's burning forms and the stove's burning efficiency, and when medium-volatile bituminous coals (MVB) are excluded from use, averaged EF(BC) and EF(OC) for bituminous coal decrease by 50% and 30%, respectively. According to these EFs, China's BC and OC emissions from the household sector in 2000 were 94 and 244 gigagrams (Gg), respectively. Compared with previous BC emission estimates for this sector (e.g., 465 Gg by Ohara et al., Atmos. Chem. Phys. 2007, 7, 4419-4444), a dramatic decrease was observed and was mainly attributed to the update of EFs. As suggested by this study, if MVB is prohibited as household fuel together with further promotion of briquettes, BC and OC emissions in this sector will be reduced by 80% and 34%, respectively, and then carbonaceous emissions can be controlled to a large extent in China.

In this study, black carbon (BC) aerosols were continuously observed using a seven-channel aethalometer (AE-33) in Ordos from August 12 to October 4, 2019; using this data combined with article matter (PM), pollutant gas, and meteorological element data; a HYSPLIT model; and potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) models, we analyzed the temporal evolution and potential source appointment and main influence areas of BC. The results showed that the average of ρ(BC) was 882 ng·m-3, accounting for 6.08% of PM2.5. The ρ(BC) was mainly concentrated at 200-1000 ng·m-3, accounting for 55.9% of the total samples. In different BC mass concentration ranges, BCliquid was the mainstay, with an average proportion of 86%. The diurnal variations in BC and PM2.5 showed unimodal distributions, with peaks at 08:00 and 10:00, respectively, and peak concentrations increased by 24.3% and 47.2%, respectively. The diurnal variation in BCsolid showed a bimodal distribution, with peaks at 08:00 and 20:00, respectively. The diurnal variation in the BCliquid showed a unimodal distribution with a peak at 08:00. The strong correlation between BC and NO2 indicated a greater impact of vehicle emissions on BC concentration, whereas the weak correlation between BC and SO2 indicated a lower impact of industrial emissions on BC concentration. The dominant air masses affecting the Ordos could be divided into four categories. The southern air masses (35.6%) had the highest mass concentration of atmospheric pollutants, followed by the local air masses (26.9%) and the northwest air masses (18.8%), and the northeast air masses (18.7%) had the lowest mass concentration of pollutants. The influence of the Ordos on the downstream areas was mainly divided into the northeast air masses (40.9%), the northwest air masses (30.4%), and the southeast air masses (28.7%). High CWT value areas of BC were mainly located in the southern Yan'an-Tongchuan-Baoji-Hanzhong areas and Lvliang-Linfen-Sanmenxia-Nanyang areas. They were two long and narrow transmission belts with a weight mass concentration exceeding 1400 ng·m-3. High CWT value areas of BC had the greatest impact on the Wuhai-Bayannaoer-Baotou-Hohhot regions, with a weight concentration exceeding 900 ng·m-3. The long-range transportation of BC could reach the Yulin-Yan'an-Tongchuan-Baoji areas in the south, the Shuozhou-Datong-Beijing areas in the east, and the Xilin Gol League-Xing'an League-Hulunbuir areas in the northeast.

Abstract. A detailed study of the levels, the temporal and diurnal variability of the main compounds involved in the biogenic sulfur cycle was carried out in Crete (Eastern Mediterranean) during the Mediterranean Intensive Oxidant Study (MINOS) field experiment in July-August 2001. Intensive measurements of gaseous dimethylsulfide (DMS), dimethylsulfoxide (DMSO), sulfur dioxide (SO2), sulfuric (H2SO4) and methanesulfonic acids (MSA) and particulate sulfate (SO42-) and methanesulfonate (MS-) have been performed during the campaign. Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol·mol-1 (mean value of 21.7 pmol·mol-1) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol·mol-1. Concurrent measurements of OH and NO3 radicals during the campaign indicate that NO3 levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol·mol-1 (mean value of 1.7 pmol·mol-1) and presents a diurnal variation similar to that of DMS. SO2 levels ranged from 220 to 2970 pmol·mol-1 (mean value of 1030 pmol·mol-1), while nss-SO42- and MS- ranged from 330 to 7100 pmol·mol-1, (mean value of 1440 pmol·mol-1) and 1.1 to 37.5 pmol·mol-1 (mean value of 11.5 pmol·mol-1) respectively. Of particular interest are the measurements of gaseous MSA and H2SO4. MSA ranged from below the detection limit (3x104) to 3.7x107 molecules cm-3, whereas H2SO4 ranged between 1x105 and 9.0x107 molecules cm-3. The measured H2SO4 maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO2 levels in the area. From the concurrent SO2, OH, and H2SO4 measurements a sticking coefficient of 0.52±0.28 was calculated for H2SO4. From the concurrent MSA, OH, and DMS measurements the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to range between 0.1-0.4%. This low MSA yield implies that gaseous MSA levels can not account for the observed MS- levels. Heterogeneous reactions of DMSO on aerosols should be considered to explain the observed levels of MS-.

Morphological and chemical properties of black carbon in physical soil fractions as revealed by scanning electron microscopy and energy-dispersive X-ray spectroscopy

Black carbon (BC) aerosols were observed over Xi'an (XA) and Hong Kong (HK) to better compare its properties and sources in two geographically separate regions in China. High-BC (7.9 ± 3.3μg·m-3) and -PM2.5 (182 ± 80.5μg·m-3) concentrations were observed in XA, and these were much higher than those in HK (BC, 3.2 ± 0.9μg·m-3; PM2.5, 34.5 ± 9.3μg·m-3). The contribution of BC to PM2.5 in HK reached 10.7%, which was ~ 1.5 times than that in XA (7.6%). The results emphasized that BC played an important role in HK PM2.5. The diurnal distribution of HK BC was highly correlated with vehicle emissions during the daytime; it peaked during heavy traffic times. Whereas XA BC exhibited flat distribution owing to stable BC sources. It is not markedly driven by traffic patterns. Additionally, the potential source contribution function (PSCF) analysis showed that XA BC mainly originated from local emissions while nearly half of the HK BC originated from distant sources, such as industrial emissions from northeastern regions and ship emissions from marine regions. These anthropogenic BC sources were found to be regional in nature based on multilinear engine (ME-2) analysis. Specifically, the XA BC sources were dominated by three factors: 22.5% from coal burning, 19.6% from biomass burning, and 32.9% from vehicle emissions. In HK, the majority of BC contributions originated from vehicle and ship emissions (78.9%), while only 14.5% and 1.5% originated from coal and biomass burning from residential combustion, as well as industrial and power plants in inland China.

Particulate black carbon mass concentrations and the episodic source identification driven by atmospheric blocking effects in Astana, Kazakhstan