Abundance and Light Absorption Properties of Brown Carbon Emitted from Residential Coal Combustion in China.

Brown carbon (BrC) fractions, including water-soluble organic carbon (WSOC), water-soluble humic-like substances (HULISw), alkaline soluble organic carbon (ASOC), and methanol soluble organic carbon (MSOC) were extracted from particles emitted from the residential combustion of coal with different geological maturities. The abundances and light absorption properties of these BrC fractions were comprehensively studied. The results showed that the abundances of the different constituents of the BrC fraction varied greatly with the extraction solvent, accounting for 4.3%-46%, 2.3%-23%, 3.2%-14%, and 76%-98% of the total carbon content in particles. The specific UV-vis absorbance (SUVA254) of BrC fractions followed the order of MSOC > ASOC > HULISw > WSOC. The WSOC and MSOC fractions from the combustion of low maturity coal had relatively low SUVA254 and high SR values. The mass absorption efficiencies (MAE365) for ASOC and MSOC were higher than for WSOC, and WSOC and MSOC from low maturity coal combustion had relatively low levels of light absorption. These findings indicated that coal combustion is a potential source of atmospheric BrC and the abundance and light absorption of the coal combustion-derived BrC fractions were strongly dependent on the extraction methods used and the coal maturity rather than the coal shapes.

Molecular Characterization of Water-Soluble Humic like Substances in Smoke Particles Emitted from Combustion of Biomass Materials and Coal Using Ultrahigh-Resolution Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Water-soluble humic like substances (HULIS) in smoke particles emitted from combustion of biomass materials and coal were characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. The formulas identified were classified into four main groups: CHO, CHON, CHOS, and CHONS. The average H/C and O/C ratios are 1.13-1.33, 1.01-1.13, 1.26-1.48, 1.09-1.24 and 0.21-0.41, 0.27-0.45, 0.41-0.46, 0.44-0.61 for the CHO, CHON, CHOS, and CHONS groups, respectively. The CHO compound was the predominant component (43%-72%) of the smoke HULIS from biomass burning (BB) and coal combustion, followed by the CHON group for BB-smoke HULIS and the S-containing groups (i.e., CHOS and CHONS) for coal-smoke HULIS. These results indicate that the primary HULIS emitted from biomass burning contain a high abundance of CHON species, which appear to be made up mainly of oxidized nitrogen functional groups such as nitro compounds and/or organonitrates. The coal-smoke HULIS contained more compounds with relatively low molecular weight and high aromaticity index (AImod). They were significantly enriched in S-containing compounds with high double bond equivalent (≥4), and O/S ratios suggest that they are most likely made up of aromatic organosulfates and nitrooxy organosulfates that are usually found in polluted atmospheres. These findings imply that the primary emissions from combustion of biomass and coal fuels are potential sources of water-soluble HULIS in an atmospheric matrix and that coal combustion is an especially important source of sulfate compounds.

Emission and Size Distribution of Particle-bound Polycyclic Aromatic Hydrocarbons from Residential Wood Combustion.

Emissions and size distributions of 28 particle-bound polycyclic aromatic hydrocarbons (PAHs) from residential combustion of 19 fuels in a domestic cooking stove in rural China were studied. Measured emission factors of total PAHs were 1.79±1.55, 12.1±9.1, and 5.36±4.46 mg/kg for fuel wood, brushwood, and bamboo, respectively. Approximate 86.7, 65.0, and 79.7% of the PAHs were associated with fine particulate matter with size less than 2.1 µm for these three types of fuels. Statistically significant difference in emission factors and size distributions of particle-bound PAHs between fuel wood and brushwood was observed, with the former had lower emission factors but more PAHs in finer PM. Mass fraction of the fine particles associated PAHs was found to be positively correlated with fuel density and moisture, and negatively correlated with combustion efficiency. Low and high molecular weight PAHs segregated into the coarse and fine PM, respectively. The high accumulation tendency of the PAHs from residential wood combustion in fine particles implies strong adverse health impact.

Emission characteristics for polycyclic aromatic hydrocarbons from solid fuels burned in domestic stoves in rural China.

Emission characterization of polycyclic aromatic hydrocarbons (PAHs) from residential combustion of crop residues, woody material, coal, and biomass pellets in domestic stoves in rural China are compared in term of emission factors (EFs), influencing factors, composition profiles, isomer ratios and phase distributions. The EFs of PAHs vary by 2 orders of magnitude among fuel types suggesting that a detailed fuel categorization is useful in the development of an emission inventory and potential in emission abatement of PAHs by replacing dirty fuels with relatively cleaner ones. The influence of fuel moisture in biomass burning is nonlinear. Biofuels with very low moisture display relatively high emissions as do fuels with very high moisture. Bituminous coals and brushwood yield relatively large fractions of high molecular PAHs. The emission factor of benzo(a)pyrene equivalent quantity for raw bituminous coal is as high as 52 mg/kg, which is 1-2 orders of magnitude higher than the other fuels. For source diagnosis, high molecular weight isomers are more informative than low molecular weight ones and multiple ratios could be used together whenever possible.

Field measurement of emission factors of PM, EC, OC, parent, nitro-, and oxy- polycyclic aromatic hydrocarbons for residential briquette, coal cake, and wood in rural Shanxi, China.

Air pollutants from residential solid fuel combustion are attracting growing public concern. Field measured emission factors (EFs) of various air pollutants for solid fuels are close to the reality and urgently needed for better emission estimations. In this study, emission factors of particulate matter (PM), organic carbon (OC), elemental carbon (EC), and various polycyclic aromatic hydrocarbons (PAHs) from residential combustions of coal briquette, coal cake, and wood were measured in rural Heshun County, China. The measured EFs of PM, OC, and EC were 8.1-8.5, 2.2-3.6, 0.91-1.6 g/kg for the wood burnt in a simple metal stove, 0.54-0.64, 0.13-0.14, 0.040-0.0041 g/kg for the briquette burned in an improved stove with a chimney, and 3.2-8.5, 0.38-0.58, 0.022-0.052 g/kg for the homemade coal cake combusted in a brick stove with a flue, respectively. EFs of 28 parent PAHs, 4 oxygenated PAHs, and 9 nitro-PAHs were 182-297, 7.8-10, 0.14-0.55 mg/kg for the wood, 14-16, 1.7-2.6, 0.64-0.83 mg/kg for the briquette, and 168-223, 4.7-9.5, 0.16-2.4 mg/kg for the coal cake, respectively. Emissions from the wood and coal cake combustions were much higher than those for the coal briquette, especially true for high molecular weight PAHs. Most EFs measured in the field were higher than those measured in stove combustions under laboratory conditions.

Influence of fuel moisture, charge size, feeding rate and air ventilation conditions on the emissions of PM, OC, EC, parent PAHs, and their derivatives from residential wood combustion.

Controlled combustion experiments were conducted to investigate the influence of fuel charge size, moisture, air ventilation and feeding rate on the emission factors (EFs) of carbonaceous particulate matter, parent polycyclic aromatic hydrocarbons (pPAHs) and their derivatives from residential wood combustion in a typical brick cooking stove. Measured EFs were found to be independent of fuel charge size, but increased with increasing fuel moisture. Pollution emissions from the normal burning under an adequate air supply condition were the lowest for most pollutants, while more pollutants were emitted when an oxygen deficient atmosphere was formed in the stove chamber during fast burning. The impacts of these factors on the size distribution of emitted particles was also studied. Modified combustion efficiency and the four investigated factors explained 68%, 72%, and 64% of total variations in EFs of PM, organic carbon, and oxygenated PAHs, respectively, but only 36%, 38% and 42% of the total variations in EFs of elemental carbon, pPAHs and nitro-PAHs, respectively.

Influence of fuel mass load, oxygen supply and burning rate on emission factor and size distribution of carbonaceous particulate matter from indoor corn straw burning.

The uncertainty in emission estimation is strongly associated with the variation in emission factor (EF), which could be influenced by a variety of factors such as fuel properties, stove type, fire management and even methods used in measurements. The impacts of these factors are complicated and often interact with each other. Controlled burning experiments were conducted to investigate the influences of fuel mass load, air supply and burning rate on the emissions and size distributions of carbonaceous particulate matter (PM) from indoor corn straw burning in a cooking stove. The results showed that the EFs of PM (EF(PM)), organic carbon (EFoc) and elemental carbon (EF(EC)) were independent of the fuel mass load. The differences among them under different burning rates or air supply amounts were also found to be insignificant (p > 0.05) in the tested circumstances. PM from the indoor corn straw burning was dominated by fine PM with diameter less than 2.1 microm, contributing 86.4% +/- 3.9% of the total. The size distribution of PM was influenced by the burning rate and air supply conditions. On average, EF(PM), EF(OC) and EF(EC) for corn straw burned in a residential cooking stove were (3.84 +/- 1.02), (0.846 +/- 0.895) and (0.391 +/- 0.350) g/kg, respectively. EF(PM), EF(OC) and EF(EC) were found to be positively correlated with each other (p < 0.05), but they were not significantly correlated with the EF of co-emitted CO, suggesting that special attention should be paid to the use of CO as a surrogate for other incomplete combustion pollutants.

Emissions of parent, nitrated, and oxygenated polycyclic aromatic hydrocarbons from indoor corn straw burning in normal and controlled combustion conditions.

Emission factors (EFs) of parent polycyclic aromatic hydrocarbons (pPAHs), nitrated PAHs (nPAHs), and oxygenated PAHs (oPAHs) were measured for indoor corn straw burned in a brick cooking stove under different burning conditions. The EFs of total 28 pPAHs, 6 nPAHs and 4 oPAHs were (7.9 +/- 3.4), (6.5 +/- 1.6) x 10(-3), and (6.1 +/- 1.4) x 10(-1) mg/kg, respectively. Fuel charge size had insignificant influence on the pollutant emissions. Measured EFs increased significantly in a fast burning due to the oxygen deficient atmosphere formed in the stove chamber. In both restricted and enhanced air supply conditions, the EFs of pPAHs, nPAHs and oPAHs were significantly higher than those measured in normal burning conditions. Though EFs varied among different burning conditions, the composition profiles and calculated isomer ratios were similar, without significant differences. The results from the stepwise regression model showed that fuel burning rate, air supply amount, and modified combustion efficiency were the three most significant influencing factors, explaining 72%-85% of the total variations.

Retene emission from residential solid fuels in China and evaluation of retene as a unique marker for soft wood combustion.

Retene (1-methyl-7-isopropylphenanthrene) is often used as a marker for softwood combustion and for polycyclic aromatic hydrocarbon (PAH) source apportionment. The emission factors of retene (EF(RET)s) from 11 crop residues, 27 firewood fuels, and 5 coals were measured using traditional rural Chinese stoves. Retene was measured in combustion emissions from all of the residential fuels tested and EF(RET)s varied significantly among the fuels due to the differences in fuel properties and combustion conditions. EF(RET)s for pine (0.34 ± 0.08 mg/kg) and larch (0.29 ± 0.22 mg/kg) were significantly higher than those of other wood types, including fir and cypress (0.081 ± 0.058 mg/kg). However, EF(RET)s for crop residues varied from 0.048 ± 0.008 to 0.37 ± 0.14 mg/kg and were not significantly lower than those for softwood (0.074 ± 0.026 to 0.34 ± 0.08 mg/kg). The EF(RET)s for coal were very high and ranged from 2.2 ± 1.5 (anthracite briquette) to 187 ± 113 mg/kg (raw bituminous chunk). EF(RET) was positively correlated with EFs of coemitted particulate matter (EF(PM)) and phenanthrene (EF(PHE)) for crop residue and coal, but not for wood. In addition, the ratios of EF(PHE)/EF(RET) and EF(PM)/EF(RET) for coals were much lower than those for crop residues and wood. These data suggest that retene is not a unique PAH marker for softwood combustion and that coal combustion, in particular, should be taken into account when retene is used for PAH source apportionment.

Emissions of parent, nitro, and oxygenated polycyclic aromatic hydrocarbons from residential wood combustion in rural China.

Residential wood combustion is one of the important sources of air pollution in developing countries. Among the pollutants emitted, parent polycyclic aromatic hydrocarbons (pPAHs) and their derivatives, including nitrated and oxygenated PAHs (nPAHs and oPAHs), are of concern because of their mutagenic and carcinogenic effects. In order to evaluate their impacts on regional air quality and human health, emission inventories, based on realistic emission factors (EFs), are needed. In this study, the EFs of 28 pPAHs (EF(PAH28)), 9 nPAHs (EF(PAHn9)), and 4 oPAHs (EF(PAHo4)) were measured for residential combustion of 27 wood fuels in rural China. The measured EF(PAH28), EF(PAHn9), and EF(PAHo4) for brushwood were 86.7 ± 67.6, 3.22 ± 1.95 × 10(-2), and 5.56 ± 4.32 mg/kg, which were significantly higher than 12.7 ± 7.0, 8.27 ± 5.51 × 10(-3), and 1.19 ± 1.87 mg/kg for fuel wood combustion (p < 0.05). Sixteen U.S. EPA priority pPAHs contributed approximately 95% of the total of the 28 pPAHs measured. EFs of pPAHs, nPAHs, and oPAHs were positively correlated with one another. Measured EFs varied obviously depending on fuel properties and combustion conditions. The EFs of pPAHs, nPAHs, and oPAHs were significantly correlated with modified combustion efficiency and fuel moisture. Nitro-naphthalene and 9-fluorenone were the most abundant nPAHs and oPAHs identified. Both nPAHs and oPAHs showed relatively high tendencies to be present in the particulate phase than pPAHs due to their lower vapor pressures. The gas-particle partitioning of freshly emitted pPAHs, nPAHs, and oPAHs was primarily controlled by organic carbon absorption.

Reductions in emissions of carbonaceous particulate matter and polycyclic aromatic hydrocarbons from combustion of biomass pellets in comparison with raw fuel burning.

Biomass pellets are emerging as a cleaner alternative to traditional biomass fuels. The potential benefits of using biomass pellets include improving energy utilization efficiency and reducing emissions of air pollutants. To assess the environmental, climate, and health significance of replacing traditional fuels with biomass pellets, it is critical to measure the emission factors (EFs) of various pollutants from pellet burning. However, only a few field measurements have been conducted on the emissions of carbon monoxide (CO), particulate matter (PM), and polycyclic aromatic hydrocarbons (PAHs) from the combustion of pellets. In this study, pine wood and corn straw pellets were burned in a pellet burner (2.6 kW), and the EFs of CO, organic carbon, elemental carbon, PM, and PAHs (EF(CO), EF(OC), EF(EC), EF(PM), and EF(PAH)) were determined. The average EF(CO), EF(OC), EF(EC), and EF(PM) were 1520 ± 1170, 8.68 ± 11.4, 11.2 ± 8.7, and 188 ± 87 mg/MJ for corn straw pellets and 266 ± 137, 5.74 ± 7.17, 2.02 ± 1.57, and 71.0 ± 54.0 mg/MJ for pine wood pellets, respectively. Total carbonaceous carbon constituted 8 to 14% of the PM mass emitted. The measured values of EF(PAH) for the two pellets were 1.02 ± 0.64 and 0.506 ± 0.360 mg/MJ, respectively. The secondary side air supply in the pellet burner did not change the EFs of most pollutants significantly (p > 0.05). The only exceptions were EF(OC) and EF(PM) for pine wood pellets because of reduced combustion temperatures with the increased air supply. In comparison with EFs for the raw pine wood and corn straw, EF(CO), EF(OC), EF(EC), and EF(PM) for pellets were significantly lower than those for raw fuels (p < 0.05). However, the differences in EF(PAH) were not significant (p > 0.05). Based on the measured EFs and thermal efficiencies, it was estimated that 95, 98, 98, 88, and 71% reductions in the total emissions of CO, OC, EC, PM, and PAHs could be achieved by replacing the raw biomass fuels combusted in traditional cooking stoves with pellets burned in modern pellet burners.

Short Communication: Emission of Oxygenated Polycyclic Aromatic Hydrocarbons from Biomass Pellet Burning in a Modern Burner for Cooking in China.

Biomass pellets are undergoing fast deployment widely in the world, including China. To this stage, there were limited studies on the emissions of various organic pollutants from the burning of those pellets. In addition to parent polycyclic aromatic hydrocarbons, oxygenated PAHs (oPAHs) have been received increased concerns. In this study, emission factors of oPAHs (EFoPAHs) were measured for two types of pellets made from corn straw and pine wood, respectively. Two combustion modes with (mode II) and without (mode I) secondary side air supply in a modern pellet burner were investigated. For the purpose of comparison, EFoPAHs for raw fuels combusted in a traditional cooking stove were also measured. EFoPAHs were 348±305 and 396±387 µg/kg in the combustion mode II for pine wood and corn straw pellets, respectively. In mode I, measured EFoPAHs were 77.7±49.4 and 189±118 µg/kg, respectively. EFs in mode II were higher (2-5 times) than those in mode I mainly due to the decreased combustion temperature under more excess air. Compared to EFoPAHs for raw corn straw and pine wood burned in a traditional cooking stove, total EFoPAHs for the pellets in mode I were significantly lower (p < 0.05), likely due to increased combustion efficiencies and change in fuel properties. However, the difference between raw biomass fuels and the pellets burned in mode II was not statistically significant. Taking both the increased thermal efficiencies and decreased EFs into consideration, substantial reduction in oPAH emission can be expected if the biomass pellets can be extensively used by rural residents.

Influence of pyrolysis temperature and feedstock on carbon fractions of biochar produced from pyrolysis of rice straw, pine wood, pig manure and sewage sludge.

In this study, the influences of feedstock and pyrolysis temperature on carbon fractions of biochar were investigated. Four types of organic wastes (rice straw (RS), pine wood (PW), pig manure (PM) and sewage sludge (SS)) were pyrolyzed at different temperatures (300 °C, 400 °C, 500 °C, 600 °C and 700 °C). Biochar produced at low temperature exhibited high yields, high dissolved organic carbon (DOC) content and unstable organic carbon content. In contrast, biochar formed at high temperature showed high C content and C stability with a low O/C and H/C ratios. In addition, the biochar pyrolyzed from PW contained the lowest DOC of the four biochar types. The properties of DOC fractions (F1, F2 and F3) released from biochar differed depending on feedstock, pyrolysis temperatures, and extraction procedures. The highest specific ultraviolet absorbance at 254 nm of the F1 and F2 fractions were observed for RS biochar, suggesting that more aromatic organic matter was present in sequentially extracted fractions of RS biochar than in extracts from the other biochars. In addition, the hot water extracts (F2) mostly showed higher aromaticity than cold water extracts (F1). The stability of biochars was greatly enhanced at pyrolysis temperatures >500 °C. If the biochars produced in this study were to be used for carbon sequestration in soil, the first priority should be PW, followed in order by RS and PM.

Can Coronene and/or Benzo(a)pyrene/Coronene ratio act as unique markers for vehicle emission?

Coronene is a high molecular weight polycyclic aromatic hydrocarbon with seven aromatic rings. It, more specifically a lower ratio of Benzo[a]pyrene to Coronone (BaP/COR), is suggested as a marker for vehicle emission. In the present study, emissions of Coronene were measured from residential combustions of wood, crop straw, and pellets. The detection of COR in non-vehicle emission sources, and comparable BaP/COR ratios between the solid fuel combustion and vehicle emissions indicated that the generality of COR or the BaP/COR ratio as markers for the vehicle emission would be questionable, especially for the area where solid fuel combustion dominated the PAHs emission.

Field measurement on the emissions of PM, OC, EC and PAHs from indoor crop straw burning in rural China.

Field measurements were conducted to measure emission factors of particulate matter (EFPM), organic carbon (EFOC), elemental carbon (EFEC), 28 parent polycyclic aromatic hydrocarbons (EF28pPAHs), and 4 oxygenated PAHs (EF4oPAHs) for four types of crop straws burned in two stoves with similar structure but different ages. The average EFPM, EFOC, EFEC, EF28pPAHs, and EF4oPAHs were 9.1 ± 5.7 (1.8-22 as range), 2.6 ± 2.9 (0.30-12), 1.1 ± 1.2 (0.086-5.5), 0.26 ± 0.19 (0.076-0.96), 0.011 ± 0.14 (1.3 × 10(-4) - 0.063) g/kg, respectively. Much high EF28pPAHs was observed in field compared with the laboratory derived EFs and significant difference in EF28pPAHs was identified among different crop residues, indicating considerable underestimation when laboratory derived EFs were used in the inventory. The field measured EFPM, EFOC, and EFEC were significantly affected by stove age and the EFs of carbonaceous particles for the 15-year old stove were approximately 2.5 times of those for the 1-year old stove.

Dietary and inhalation exposure to polycyclic aromatic hydrocarbons and urinary excretion of monohydroxy metabolites--a controlled case study in Beijing, China.

Daily dietary and inhalation exposures to 16 parent polycyclic aromatic hydrocarbons (PAHs) and urinary excretion of 13 monohydroxy metabolites (OHPAHs) were monitored for 12 non-smoking university students in Beijing, China, during a controlled feeding experiment. The relationship between the urinary excretion of OHPAHs and the uptake of PAHs was investigated. The results suggest severe exposure of the subjects to PAHs via both dietary and inhalation pathways. Large increase of most urinary OHPAHs occurred after the ingestion of lamb kabob. Higher concentrations of OHPAHs were observed for female subjects, with the intakes of parent PAHs lower than those by males, likely due to the gender differences in metabolism. It appears that besides 1-PYR, metabolites of PHE could also be used as biomarkers to indicate the short-term dietary exposure to PAHs and urinary 3-BaA may serve as the biomarker for inhalation intake of high molecular weight PAHs.

Pollution level, inhalation exposure and lung cancer risk of ambient atmospheric polycyclic aromatic hydrocarbons (PAHs) in Taiyuan, China.

Passive air samplers were deployed to collect both gas and particulate phase polycyclic aromatic hydrocarbons in Taiyuan between 2009 and 2010. Annual average concentrations of BaP equivalent concentration (B[a]P(eq)) in background, rural and urban areas were 2.90 ± 0.29, 23.2 ± 30.8 and 27.4 ± 28.1 ng/m(3), respectively, with higher concentration in the winter than in other seasons. The median B[a]P(eq) concentrations of annual inhalation exposure were estimated to be in the range of 103-347 ng/d for all population groups in rural as well as in urban areas. The median values of incremental lifetime cancer risk (ILCR) induced by whole year inhalation exposure for all groups were basically larger than 10(-6), with higher values in winter than in other seasons and in urban than in rural area. In the same season and area, the ILCR of adults was larger than other age groups and that of females was a little higher than males.