Primary Biomass Burning Emissions Research Articles

Integration of field observation and air quality modeling to characterize Beijing aerosol in different seasons.

Fine particulate matter (PM2.5) pollution in Beijing was investigated based on field observation and air quality modeling. Measurement results showed that when using elemental carbon (EC) as the reference component, concurrent increases were observed in the relative abundances of sulfate, nitrate, organic carbon (OC) and water-soluble organic carbon (WSOC) when RH exceeded ∼65% during winter. The observed increases could not be explained by variations of primary biomass burning emissions, instead they likely pointed to heterogeneous chemistry and presumably indicated that formation of secondary inorganic and organic aerosols might be related during winter haze events in Beijing. Large gaps were found in winter when comparing the observational and modeling results. In summer, RH exhibited little influence on the observed sulfate/EC, OC/EC or WSOC/EC, and the observed and modeled results were in general comparable for the concentrations of sulfate, EC and OC. This study suggests that distinct yet poorly-understood atmospheric chemistry may be at play in China's winter haze events, and it could be a substantial challenge to properly incorporate the related mechanisms into air quality models.

The formation of nitro-aromatic compounds under high NO<sub><i>x</i></sub> and anthropogenic VOC conditions in urban Beijing, China

Abstract. Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m−3, higher than those reported in other summertime studies (0.14–6.44 ng m−3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 ∼ 20 ppb for daytime and NO2∼25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3- concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC+4M5NC) ∕ 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH > 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.

Light Absorption by Ambient Black and Brown Carbon and its Dependence on Black Carbon Coating State for Two California, USA, Cities in Winter and Summer

AbstractObservations from a wintertime and summertime field campaign are used to assess the relationship between black and brown carbon (BC and BrC, respectively) optical properties and particle composition and coating state. The wintertime campaign, in Fresno, CA, was impacted by primary emissions from residential wood burning, secondary organic and inorganic particle formation, and BC from motor vehicles. Two major types of BrC were observed in wintertime. One occurred primarily at night—the result of primary biomass burning emissions. The second was enhanced in daytime and strongly associated with particulate nitrate and the occurrence of fog. The biomass‐burning‐derived BrC absorbed more strongly than the nitrate‐associated BrC but had a weaker wavelength dependence. The wintertime BC‐specific mass absorption coefficient (MACBC) exhibited limited dependence on the ensemble‐average coating‐to‐BC mass ratio (Rcoat‐rBC) at all wavelengths, even up to Rcoat‐rBC of ~5. For the summertime campaign, in Fontana, CA, BC dominated the light absorption, with negligible BrC contribution even after substantial photochemical processing. The summertime MACBC exhibited limited dependence on Rcoat‐rBC, even up to ratios of >10. Based on the four classes of BC‐containing particles identified by Lee et al. (2017, https://doi.org/10.5194/acp‐17‐15055‐2017) for the summertime measurements, the general lack of an absorption enhancement can be partly—although not entirely—attributed to an unequal distribution of coating materials between the BC‐containing particle types. These observations demonstrate that in relatively near‐source environments, even those impacted by strong secondary aerosol production, the ensemble‐average, mixing‐induced absorption enhancement for BC due to coatings can be quite small.

Real-time assessment of wintertime organic aerosol characteristics and sources at a suburban site in northern France

A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during wintertime (5 February to 15 March 2016) at a suburban site in Douai, northern France, in order to investigate the characteristics and sources of the organic matter (OM). The campaign average concentration of non-refractory submicron particulate matter (NR-PM1) was 11.1 ± 9.3 μg m−3, and composed of 38% OM, 36% nitrate, 16% ammonium and 9% sulfate. The average values for the OM:OC, O:C and H:C ratios were 1.60 ± 0.15, 0.32 ± 0.11 and 1.55 ± 0.14, respectively, indicating a moderate level of aerosol oxidation. The positive matrix factorization (PMF) source apportionment method was applied to the high-resolution organic aerosol (OA) mass spectra, resulting in four factors: a hydrocarbon-like (HOA) factor; one associated with oxidized biomass burning (oBBOA); and two oxygenated factors (OOA) denoted as less oxidized (LO-OOA) and more oxidized (MO-OOA), with average contributions to OA of 20%, 28%, 17% and 35%, respectively. The oBBOA factor was found to be mainly local as shown by non-parametric wind regression (NWR) analysis, and to correlate well with relative humidity (RH), suggesting fast aqueous processing of locally emitted primary biomass burning emissions. During most part of the campaign, the sampling site was affected by different air masses. However, during the last period of the campaign (5–16 March 2016) the site was heavily impacted by air masses from Eastern Europe which were rich in secondary inorganic and organic aerosols. The H:C versus O:C (Van Krevelen, VK) diagram highlighted that the aerosol followed an oxidation process throughout the whole campaign, with an average slope of −1.05. The impact of continental air masses towards the end of the campaign confined the aerosol towards a narrower space in the VK diagram, suggesting a homogenization of the different aerosol sources due to OA ageing during transport. Several nocturnal NPF (new particle formation)-like events were observed and associated to the fast processing of BBOA emissions and the formation of ammonium nitrate.

The characteristics of carbonaceous aerosol in Beijing during a season of transition

Carbonaceous aerosol was measured during fall of 2010 in Beijing. Daily variation of organic carbon (OC) was found to coincide with that of relative humidity (RH), and the OC to elemental carbon (EC) ratios were more than doubled during the more humid periods (RH above 0.75) compared to other conditions. This large increase in OC/EC could not be explained by the variations of primary biomass burning emissions but was accompanied by a five-fold increase in the sulfate to EC ratio. It was then inferred that secondary organic aerosol (SOA) formation was enhanced under the more humid conditions, presumably through aqueous-phase processes. This enhanced SOA formation might be partially associated with particles externally mixed with black carbon, as indicated by the RH-dependent relationships between aerosol optical attenuation and EC loading. In addition, organic aerosols exhibited different properties between the more humid and the other periods, such that they were less volatile and charred more significantly during thermal-optical analysis in the former case. These differences coincided with the evidence of enhanced SOA formation under the more humid conditions. This study highlights the necessity of incorporating aqueous-phase chemistry into air quality models for SOA.

Optical absorption characteristics of brown carbon aerosols during the KORUS-AQ campaign at an urban site

This study investigates the absorption characteristics of brown carbon (BrC) obtained from water and methanol extracts of fine particulate matter measured at an urban site in Gwangju, Korea during the KOREA U.S. – Air Quality campaign (May 2–June 11, 2016). The measurement period was classified into two intervals: biomass burning (BB) and non-BB periods. During the non-BB period, water-soluble organic carbon (WSOC) and humic-like substances (HULIS) primarily resulted from secondary organic aerosol (SOA) formation and primary vehicle emissions. Water-soluble organic aerosols during the BB period, meanwhile, were closely related to SOA formation and regionally transported BB emissions.The light absorption coefficient measured at 365nm (babs,365) by methanol extracts was 2.6 and 6.1 times higher than the coefficients from the water and HULIS extracts, respectively, indicating the importance of BrC absorption by water-insoluble organic carbon. This was demonstrated by a good correlation between the water-insoluble BrC absorption and the elemental carbon concentration. A comparison of babs,365 between the methanol- and water-extracted BrC indicated that water-insoluble BrC accounted for approximately 61% (33–86%) of the total BrC absorption. The contributions of SOA, primary BB emissions, and traffic emissions to the water extract babs,365 were estimated using a stepwise multiple linear regression (MLR) analysis and found to be 1.17±0.55, 0.65±0.62, and 0.25±0.09Mm−1, respectively, accounting for 59.6, 26.1, and 14.3% of the absorption coefficient by the water-soluble BrC. Further, it was determined that the contribution of the BB emissions to the water-soluble BrC absorption was approximately two times higher in the BB period than in the non-BB period.The average absorption Ångstrӧm exponent was 4.8±0.3, 5.3±0.7, and 6.8±0.8 for the methanol, water, and HULIS extracts, respectively. The average mass absorption efficiency (MAE365) of methanol extracted BrC was 1.3±0.4m2/g·C. Water- and HULIS-extracted BrC had a MAE365 of 1.0±0.3 and 0.8±0.3m2/g·C, respectively. These results suggest that methanol-extracted BrC could provide a better estimation of BrC absorption compared to WSOC and HULIS.

Fossil vs. non-fossil sources of fine carbonaceous aerosols in four Chinese cities during the extreme winter haze episode of 2013

Abstract. During winter 2013, extremely high concentrations (i.e., 4–20 times higher than the World Health Organization guideline) of PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) mass concentrations (24 h samples) were found in four major cities in China including Xi'an, Beijing, Shanghai and Guangzhou. Statistical analysis of a combined data set from elemental carbon (EC), organic carbon (OC), 14C and biomass-burning marker measurements using Latin hypercube sampling allowed a quantitative source apportionment of carbonaceous aerosols. Based on 14C measurements of EC fractions (six samples each city), we found that fossil emissions from coal combustion and vehicle exhaust dominated EC with a mean contribution of 75 ± 8% across all sites. The remaining 25 ± 8% was exclusively attributed to biomass combustion, consistent with the measurements of biomass-burning markers such as anhydrosugars (levoglucosan and mannosan) and water-soluble potassium (K+). With a combination of the levoglucosan-to-mannosan and levoglucosan-to-K+ ratios, the major source of biomass burning in winter in China is suggested to be combustion of crop residues. The contribution of fossil sources to OC was highest in Beijing (58 ± 5%) and decreased from Shanghai (49 ± 2%) to Xi'an (38 ± 3%) and Guangzhou (35 ± 7%). Generally, a larger fraction of fossil OC was from secondary origins than primary sources for all sites. Non-fossil sources accounted on average for 55 ± 10 and 48 ± 9% of OC and total carbon (TC), respectively, which suggests that non-fossil emissions were very important contributors of urban carbonaceous aerosols in China. The primary biomass-burning emissions accounted for 40 ± 8, 48 ± 18, 53 ± 4 and 65 ± 26% of non-fossil OC for Xi'an, Beijing, Shanghai and Guangzhou, respectively. Other non-fossil sources excluding primary biomass burning were mainly attributed to formation of secondary organic carbon (SOC) from non-fossil precursors such as biomass-burning emissions. For each site, we also compared samples from moderately to heavily polluted days according to particulate matter mass. Despite a significant increase of the absolute mass concentrations of primary emissions from both fossil and non-fossil sources during the heavily polluted events, their relative contribution to TC was even decreased, whereas the portion of SOC was consistently increased at all sites. This observation indicates that SOC was an important fraction in the increment of carbonaceous aerosols during the haze episode in China.