Indoor air pollution from the household combustion of coal: Tempo-spatial distribution of gaseous pollutants and semi-quantification of source contribution.

Coal is a widely used solid fuel for cooking and heating activities in rural households, whose incomplete combustion in inefficient household stoves releases a range of gaseous pollutants. To evaluate the impact of coal combustion on indoor air quality, this study comprehensively investigated the indoor air pollution of typical gaseous pollutants, including formaldehyde (HCHO), carbon dioxide (CO2), carbon monoxide (CO), total volatile organic compounds (TVOC), and methane (CH4), during coal combustion process in rural households using online monitoring with high tempo-spatial resolution. The indoor concentrations of gaseous pollutants were considerably elevated during the coal combustion period, with the indoor concentrations being significantly higher than those in courtyard air. The levels of several gaseous pollutants (CO2, CO, TVOC, and CH4) in indoor air were much higher during the flaming phase than the de-volatilization and smoldering phases, while HCHO peaked in the de-volatilization phase. The gaseous pollutant concentrations mostly decreased from the room ceiling to the ground level, while their horizontal distribution was relatively uniform within the room. It was estimated that coal combustion accounted for about 71 %, 92 %, 63 %, 59 %, and 21 % of total exposure to indoor CO2, CO, TVOC, CH4, and HCHO, respectively. Improved stove combined with clean fuel could effectively lower the concentrations of CO2, CO, TVOC, and CH4 in indoor air and reduce the contributions of coal combustion to these gaseous pollutants by about 21-68 %. These findings help better understand the indoor air pollution resulting from residential coal combustion and could guide the development of intervention programs to improve indoor air quality in rural households of northern China.

Atmospheric ammonia in the rural North China Plain during wintertime: Variations, sources, and implications for HONO heterogeneous formation.

Atmospheric ammonia (NH3) plays an important role in secondary inorganic aerosol formation. Understanding the temporal variations, sources, and environmental influences of NH3 is conducive to better formulate PM2.5 pollution control strategies for policy-makers. Here, we performed a comprehensive field campaign with the measurements of NH3 and related parameters at a rural site of the North China Plain (NCP) in winter of 2017. The results showed that residential coal combustion contributed dominantly to NH3 during the entire observation period, resulting in the obviously high average concentration of NH3 (31.2 ± 24.6 ppbv). The sensitivity tests of pH-NHx during the three different pollution periods suggested that the rural site was always in the NHx-rich atmosphere where high levels of NHx increased the particle pH inefficiently. Nevertheless, the particle pH still elevated by 1.5-2.2 units at the excessive NHx levels during the three pollution periods. In addition, the HONO/NO2 ratios were found to correlate linearly with NH3 concentrations, implying the acceleration effect of NH3 on HONO production from NO2 heterogeneous reactions. After considering the NH3-enhanced uptake coefficient of NO2 in the nocturnal HONO budget, the unknown source of HONO could be fully explained. Therefore, more attentions should be given for effective emission control of NH3 to improve air quality throughout the NCP, especially in the rural areas.

Socioeconomic and Demographic Associations with Wintertime Air Pollution Exposures at Household, Community, and District Scales in Rural Beijing, China.

The Chinese government implemented a national household energy transition program that replaced residential coal heating stoves with electricity-powered heat pumps for space heating in northern China. As part of a baseline assessment of the program, this study investigated variability in personal air pollution exposures within villages and between villages and evaluated exposure patterns by sociodemographic factors. We randomly recruited 446 participants in 50 villages in four districts in rural Beijing and measured 24 h personal exposures to fine particulate matter (PM2.5) and black carbon (BC). The geometric mean personal exposure to PM2.5 and BC was 72 and 2.5 µg/m3, respectively. The variability in PM2.5 and BC exposures was greater within villages than between villages. Study participants who used traditional stoves as their dominant source of space heating were exposed to the highest levels of PM2.5 and BC. Wealthier households tended to burn more coal for space heating, whereas less wealthy households used more biomass. PM2.5 and BC exposures were almost uniformly distributed by socioeconomic status. Future work that combines these results with PM2.5 chemical composition analysis will shed light on whether air pollution source contributors (e.g., industrial, traffic, and household solid fuel burning) follow similar distributions.

Investigating the relationship between mass concentration of particulate matter and reactive oxygen species based on residential coal combustion source tests.

Particulate matter (PM) has been considered to be closely related to human health, especially fine particulate matter. However, whether PM mass concentration alone is a good indicator for health impact remains a challenging question. In this study, emissions from residential coal combustion (RCC), one of the important PM sources in northern China, were tested to examine the relationship between the emission factors of particle-generated reactive oxygen species (ROS) (EFROS) and PM (EFPM). A total of 24 combinations of source tests were conducted, including eight types of coal with different geological maturities (two anthracites and six bituminous) burned in three types of stoves (one honeycomb coal stove, one old chunk stove, and one new chunk stove). Here, ROS was defined as generated hydroxyl radical (·OH) by PM, and results showed EFROS from 24 residential coal combustion varied greatly by nearly 20 times. EFROS ranged 0.78-14.85 and 2.99-12.91 mg kg-1 for the emissions from honeycomb and chunk coals, respectively. Moreover, the correlation between EFROS and EFPM was significantly positive in honeycomb coal emissions (r = 0.82, p < 0.05), but it was insignificant in chunk coal emissions (r = 0.07, p > 0.05). For honeycomb coal emissions, organic carbon (OC) was quite abundant in PM and it might be the predominant contributor to both EFPM and EFROS, resulting in a strong and positive correlation. For chunk coal emissions, high EFROS was mainly related to relatively high metal emissions in AN and LVB, while the metals were not major components in PM, leading to a poor correlation between EFPM and EFROS. Therefore, this study revealed that PM was not always positively correlated with ROS from residential coal burning, and the relationship was mainly determined by the compositions of PM, suggesting PM mass concentration alone may not be the best indicator for assessing health impacts.

Refined source apportionment of residential and industrial fuel combustion in the Beijing based on real-world source profiles.

Residential and industrial emissions are considered as dominant contributors to ambient fine particulate matter (PM2.5) in China. However, the contributions of residential and industrial fuel combustion are difficult to distinguish because specific source indicators are lacking. In this study, real-world source testing was performed on residential coal, biomass and industrial combustion, industrial processes, and diesel and gasoline vehicle source emissions in the Beijing-Tianjin-Hebei region, China. PM2.5 emission factors and chemical profiles, including 97 compositions (e.g., carbonaceous matter, water-soluble ions, elements, EPA priority polycyclic aromatic hydrocarbons (EPAHs), methyl PAHs (MPAHs), and n-alkanes) were obtained for the aforementioned sources. The results showed high OC1, OC2, fluoranthene, methyl fluoranthene, and retene in emissions from residential coal combustion, high OC3, sulfate, Ca, and iron abundance in emissions from industrial combustion, and high Pb and Zn loadings in emissions from industrial processes. Furthermore, specific diagnostic ratios were determined to distinguish between residential and industrial fuel combustion. For example, the ratios of MPAHs/EPAHs (>1) and Mfluo/Fluo (>5) can be used as fingerprinting ratios to distinguish residential coal combustion from other sources. Finally, 1-h resolution refined source apportionments of PM2.5 were conducted in Beijing during two haze events (EP1 and EP2) with a chemical mass balance (CMB) model based on the localized real-world source profiles established in this study. Source apportionment results of CMB showed that the contributions of industrial and residential fuel combustion were 19.4% and 30.8% in EP1 and 26.8% and 18.1% in EP2, respectively, which were comparable to the results of the positive matrix factorization model (R2 = 0.82). This study provides valuable information for the successful and accurate determination of the contributions of residential and industrial fuel combustion to ambient PM2.5.

Source profiles of molecular structure and light absorption of PM2.5 brown carbon from residential coal combustion emission in Northwestern China.

Residential coal combustion is a prominent source of brown carbon (BrC) aerosols, but knowledge of their molecular structures and optical absorption were limited, which have notable used in ambient BrC source identification and radiative forcing calculation. In this study, the Fourier transform-ion cyclotron resonance mass spectrometry combined with partial least squares regression analysis as well as Fourier transform infrared spectroscopy analysis were used to insight the molecular compounds and structures of BrC from anthracite and bituminous coal combustions between traditional and improved stoves. The absorption Ångström exponents (AAE) and mass absorption efficiency (MAE) values for the BrC emitted from the combinations of bituminous were both 1.2-2.5 times lower than those of anthracite, interpreting that the BrC from the anthracite emissions had greater light-absorbing capacity. In contrast, the emission factor of light absorption (EFAbs) at 365 nm for the bituminous coal combusted in the traditional stove was the highest among all the tested scenarios, which revealed that the incomplete combustion of bituminous coal could emit more BrC. It was noted that primary BrC emitted from the coal combustion with traditional stoves contains higher aromaticity groups of C-C and C＝O and higher S containing organics, whereas more aliphatic groups were found in BrC using the improved stoves. N-containing (CHON and CHONS) compounds were dominated in the total molecular formula of BrC, whereas the sum of CHON and CHO groups had high double-bond equivalent (DBE) values contributed 53.5%-87.1% to the total BrC absorption. Moreover, for CHOS, the lowest of estimated molecular absorption, DBE, and DBE/C should attribute to the non-chromophoric or weak absorptive S-containing compounds. This study supplied an effective evaluation method to compare BrC emissions and their absorption for coal combustion on regional scale.

Emission and spatialized health risks for trace elements from domestic coal burning in China.

Residential coal combustion (RCC) emission exhibited obvious daily variation, while no real-time estimation of air pollutants from RCC has been reported, as the shortages of corresponding activity dataset and emission factors with high time resolution. A real-time monitoring platform for RCC emission was established. Hourly emission factors of 18 typed of TEs from eleven kinds of chunk coals and nine kinds of honeycomb coals burning in China were obtained. The monthly and hourly coal consumption amounts were calculated with reference and our field survey. Then the hourly TEs emission inventories from RCC were established in China. GEOS-Chem and Risk Quotients Models were utilized to map the spatialized health risks of hazardous elements, including the gridded hazard index and carcinogenic risk. The result indicated that the EFs of TEs would be underestimated if the tests only consider flaming conditions. Cu, K, Ca, Zn, and Co were the top five elements from RCC, with corresponding emission amounts as 1397.7, 1054.0, 676.0, 623.5 and 420 tons in 2017, respectively. K, Ti, Fe, Sn, and Sb showed hourly peak values under flaming dominated periods, accounting for 48.2%, 45.9%, 31.8%, 42.8%, and 33.8% of their daily emissions. Other elements (e.g., V, Co, As, Hg and Pb) exhibited higher emissions under smoldering dominated period in nighttime, accounting for 22.2%, 32.9%, 27.6%, 34.7%, and 28.4% of their daily emissions. TEs emission from RCC closely follows the habits of human daily cooking and heating activity. The national HI were lower than the acceptable level (HI ≤ 1) except Sichuan Province (up to 1.2). Higher carcinogenic risks (≥1 × 10-6) occurred in parts of Sichuan, Shanxi, Hunan and Hubei, which were up to 2.0 × 10-5. The high-resolution TEs emission inventories could be useful for future modeling works on the formation and evolution of air pollution and are helpful for human exposure assessment.

Hourly emission estimation of black carbon and brown carbon absorption from domestic coal burning in China.

Residential coal combustion (RCC) emission demonstrates obvious daily variation, while no real-time estimation of air pollutants from RCC has been reported, as the limitation of hourly activity data and emission factors. With a dilution sampling system, a high-precision electronic balance, and an Aethalometer Model AE33, a real-time monitoring platform for RCC emission was established. Hourly emission factors (EFs) of BC and absorption emission factors (AEFs) of BrC from eleven kinds of chunk coals and nine kinds of honeycomb coals burning in China were obtained. The monthly and hourly coal consumption amounts were calculated with the activity data from literature reviews and a field survey. The first hourly BC and absorption cross section of BrC emission inventories from RCC were established in China. The historical emission trends (2003-2017) indicated that the policy has rapidly controlled the emission of BC and ACSBrC from RCC in urban area (26.7% and 31.8% decreased, respectively in 2013). While in rural areas, their emission continually increased by 1.2% ~ 5.3% until more strict law enacted in 2017. Emissions of BC and ACSBrC in winter seasons were 60.1 Gg and 1064.1 Gm2, which accounted for 54.3% and 55.1% of the total BC and ACSBrC emissions correspondingly. The peak values of hourly emission of BC and ACSBrC (in 370 nm) normally appeared at 19:00-23:00, accounting for 43.0% and 41.5% of their total daily emission. The low emission periods were at cooking times including 7:00, 12:00, and 17:00 of a day and the whole emission of BC and ACSBrC for the three periods accounted for 1.8% and 2.3% of their daily emission. This high-resolution BC and ACSBrC emission inventories can be useful for future modeling works on the formation and evolution of a haze event, the smoke aging and transportation, as well as corresponding climate and human health effects.

Pollution levels, composition characteristics and sources of atmospheric PM2.5 in a rural area of the North China Plain during winter.

The pollution levels, composition characteristics and sources of atmospheric PM2.5 were investigated based on field measurement at a rural site in the North China Plain (NCP) from pre-heating period to heating period in winter of 2017. The hourly average concentrations of PM2.5 frequently exceeded 150 µg/m3 and even achieved 400 µg/m3, indicating that the PM2.5 pollution was still very serious despite the implementation of stricter control measures in the rural area. Compared with the pre-heating period, the mean concentrations of organic carbon (OC), element carbon (EC) and chlorine ion (Cl-) during the heating period increased by 20.8%, 36.6% and 38.8%, accompanying with increments of their proportions in PM2.5 from 37.5%, 9.8% and 5.5% to 42.9%, 12.7% and 7.2%, respectively. The significant increase of both their concentrations and proportions during the heating period was mainly ascribed to the residential coal combustion. The proportions of sulfate, nitrate and ammonium respectively increased from 9.9%, 10.9% and 9.0% in nighttime to 13.8%, 16.2% and 11.1% in daytime, implying that the daytime photochemical reactions made remarkable contributions to the secondary inorganic aerosols. The simulation results from WRF-Chem revealed that the emission of residential coal combustion in the rural area was underestimated by the current emission inventory. Six sources identified by positive matrix factorization (PMF) based on the measurement were residential coal combustion, secondary formation of inorganic aerosols, biomass burning, vehicle emission and raising dust, contributing to atmospheric PM2.5 of 40.5%, 21.2%, 16.4%, 10.8%, 8.6% and 2.5%, respectively.

Parent, alkylated, oxygenated and nitro polycyclic aromatic hydrocarbons from raw coal chunks and clean coal combustion: Emission factors, source profiles, and health risks.

Residential coals are still inevitable using in developing areas in China. Clean coal briquettes, normally using alkaline substance such as lime or red mud (RM) as the additive, were helpful in pollution emission reduction even without changes of stoves. Studies of atmospheric polycyclic aromatic hydrocarbons (PAHs) emission characteristics from RM clear coal combustion were limited. In this study, emission factors (EFs), sources profiles, and health risks of polycyclic aromatic hydrocarbons (PAHs) in PM2.5 were investigated for raw coal chunks and clean coal (with red mud) through combustion experiments. EFs of total PAHs were found to be 160.1 ± 100.9 mg·kg-1 and 19.4 ± 6.1 mg·kg-1 for bituminous and anthracite raw coal chunks (B-C and A-C), respectively. EFs values were highest for parent PAHs (p-PAHs), followed by oxygenated PAHs (o-PAHs), alkylated PAHs (a-PAHs), and nitro PAHs (n-PAHs). EFs of p-PAHs account for 80% and 52% of total PAHs emissions for B-C and A-C, respectively, while those for o-PAHs are 22.9% and 44.9%, demonstrating residential coal combustion as a significant primary source for p-PAHs and o-PAHs. Clean coals were developed through cold-press technology with red mud (RM) as additive, and clean coals with RM contents of 10% are referred to as B-10% (bituminous) and A-10% (anthracite). Compared to raw coals chunks, EFs were reduced from 128.1, 2.5, 29.3 mg·kg-1 and 161.8 µg·kg-1 to 83.5, 1.3, 16.4 mg·kg-1 and 102.2 µg·kg-1 by B-10%, and from 10.1, 0.6, 8.7 mg·kg-1 and 20.6 µg·kg-1 to 11.9, 0.2, 2.4 mg·kg-1 and 15.3 µg·kg-1 by A-10% for p-PAHs, o-PAHs, a-PAHs and n-PAHs, respectively. Diagnostic ratios of 5-Nitroacenaphthene / Acenaphthene (0.02-0.05 for coal, 0.0002 for biomass) can be used to separate residential coal and biomass burning in source analysis. When B-C was replaced by B-10%, both noncancer (0.58 to 0.33 for male, 1.65 to 0.95 for female in hazard quotient) and cancer risks (5.68 × 10-4 to 2.73 × 10-4 for male, 2.63 × 10-3 to 1.27 × 10-3 for female) can be reduced. o-PAHs should be paid more attention because of its high cancer risks caused by 6H-Benzo(C,D)Pyrene-6-One (1.74 × 10-5 for male, 8.07 × 10-5 for female), which are even more than the total risks caused by n-PAHs (3.59 × 10-7 for male, 1.66 × 10-6 for female). Results from this study highlighted the environment and health effects of PAHs originated from residential coal combustion, and proposed an effective way by using clean coal to alleviate the associated negative impacts.

Dual-modelling-based source apportionment of NOx in five Chinese megacities: Providing the isotopic footprint from 2013 to 2014.

In China, nitrate (NO3-) becomes the main contributor to fine particles (PM2.5) because the emissions of its precursor, nitrogen oxides (NOx), were not recognized and controlled well in recent years. In this work, sources, conversion, and geographical origin of NOx were interpreted combining the isotopic information (δ15N and δ18O) of NO3- and dual modelling at five Chinese megacities (Beijing, Shanghai, Guangzhou, Wuhan and Chengdu) during 2013-2014. Results showed that the δ15N-NO3- values (n = 512) ranged from -12.3‰ to +22.9‰, and the average δ18O-NO3- value was +83.4‰ ± 17.2‰. The isotopic compositions both had a rising tendency as ambient temperature dropped, attributing largely to the source changes. Bayesian model indicated the percentage for the OH pathway of NOx conversion had a clear seasonal variation with a higher value during summer (58.0% ± 9.82%) and a lower value during winter (11.1% ± 3.99%); it was also significantly correlated with latitude (p < 0.01). Coal combustion was the most important source of NOx (31.1%-41.0%), which was geographically derived from North China and other south-central developed regions implied by Potential Source Contribution Function (PSCF). Apart from Chengdu, mobile sources was the second largest contributor to NOx. This source was extensive but uniformly distributed all around the typical urban agglomerations of China. Biomass burning and microbial processes shared similar source areas, mostly originating from the North China Plain and Sichuan Basin. Based on the NOx features, we infer that residential coal combustion was the primary source of heavy PM2.5 pollution in Chinese megacities. Controlling the source categories of these regional priorities would help mitigate atmospheric pollution in these areas.

[Source Apportionment of PM2.5 in Suburban Area of Beijing-Tianjin-Hebei Region in Autumn and Winter].

To identify the main sources of PM2.5 in Beijing-Tianjin-Hebei (BTH) region, PM2.5 samples were collected at four suburban sites in BTH region during autumn and winter in 2014-2015. Source apportionment of PM2.5 was conducted using the chemical mass balance model (CMB). It shows that the main sources of PM2.5 in autumn and winter were secondary aerosols (36%-58%), traffic (8%-26%), residential coal combustion (8%-16%), and biomass burning (5%-16%). Secondary nitrate was the most important source of PM2.5 at most sites during autumn and winter (11%-27%). The source apportionment at different pollution levels indicates that the coherence of the increasing trend of different sources among the four sites were much more obvious in autumn than in winter. Also, the increasing contribution of secondary sources (47.2-115.7 µg·m-3) was much higher than that of primary sources (29.5-43.4 µg·m-3) in autumn, but such trend was not significant in winter. The total contribution of coal combustion at suburban sites was quite similar to that in urban sites, but in suburban areas residential coal combustion dominates the contribution from coal combustion. Thus, it is very necessary for suburban areas of the BTH region to control emissions from residential coal combustion.

Chemical nature of PM2.5 and PM10 in Xi'an, China: Insights into primary emissions and secondary particle formation.

In Xi'an, a city that frequently experiences serious PM pollution in northern China, 1476 PM10 and 1464 PM2.5 valid daily filter samples were collected at six sites from December 2014 to November 2015 and analyzed for 29 species. The annual mean PM10 and PM2.5 concentrations were 149.4 ±â€¯93.1, 108.0 ±â€¯70.9 µg/m3, respectively. Organic carbon (OC) is the predominant PM2.5 component while crustal material predominated in PM10. Sulfate concentrations, which was the largest component in Xi'an PM in previous studies, were lower than nitrate. Winter sulfate, OC, and elemental carbon (EC) have decreased since 2003, while nitrate remained constant in recent years and the ratio of NO3-/SO42- increased from 0.4 in 2006 to 1.3 in 2014. This result suggests that the motor vehicle contribution to PM has increased relative to coal-fired power plant emissions over the past decade. The mass fractions of crustal material, sulfate, and EC in PM2.5 decreased as the PM2.5 concentrations increased from "clean" days (<50 µg/m3) to the highest values, while nitrate significantly increased. Despite forming through secondary reactions, the high concentrations of SOC and SO42- in winter are attributed to primary emissions and particularly to residential heating and cooking with coal. Primary SOC and SO42- accounted for 33% and 42% of their total PM2.5 concentrations in winter, respectively. Therefore, control measures applied to these primary sources can substantially improve air quality.

[Emission Characteristics of Residential Coal Combustion Flue Gas in Beijing].

Honeycomb briquet,biomass briquettes and bituminous coal from suburb of Beijing were chosen as testing samples to carry out combustion experiments. The characteristics of inorganic pollutant emission factors and VOCs emission factors released from the flue gas were studied. The results showed that under the condition of sufficient combustion, the average emission factors of SO2 from these three types of coal respectively were 1.50,1.91,1.62 kg·t-1;NOx 0.420,0.901,2.20 kg·t-1;CO 22.4,37.3,87.3 kg·t-1. Combustion emission factors of gaseous pollutants for NOx and CO were in the order of bituminous coal > biomass briquettes > honeycomb briquet. SO2 emission factors were in the order of biomass briquettes > bituminous coal > honeycomb briquet. The 2014 emissions inventory of the three civil coal combustion pollutants in Beijing was obtained. Bituminous coal emissions of SO2 was more than 5.5×103 tons,NOx was more than 7.5×103 tons,CO was more than 290×103 tons. All these coal types released more kinds and higher concentrations of volatile organic compounds in ignition phase and damp down stage. VOCs emission factor was the highest during ignition phase, followed by damp down phase.

Emission factors and particulate matter size distribution of polycyclic aromatic hydrocarbons from residential coal combustions in rural Northern China.

Coal consumption is one important contributor to energy production, and is regarded as one of the most important sources of air pollutants that have considerable impacts on human health and climate change. Emissions of polycyclic aromatic hydrocarbons (PAHs) from coal combustion were studied in a typical stove. Emission factors (EFs) of 16 EPA priority PAHs from tested coals ranged from 6.25 ± 1.16 mg kg-1 (anthracite) to 253 ± 170 mg kg-1 (bituminous), with NAP and PHE dominated in gaseous and particulate phases, respectively. Size distributions of particulate phase PAHs from tested coals showed that they were mostly associated with particulate matter (PM) with size either between 0.7 and 2.1 µm or less than 0.4 µm (PM0.4). In the latter category, not only were more PAHs present in PM0.4, but also contained higher fractions of high molecular weight PAHs. Generally, there were more than 89% of total particulate phase PAHs associated with PM2.5. Gas-particle partitioning of freshly emitted PAHs from residential coal combustions were thought to be mainly controlled by absorption rather than adsorption, which is similar to those from other sources. Besides, the influence of fuel properties and combustion conditions was further investigated by using stepwise regression analysis, which indicated that almost 57 ± 10% of total variations in PAH EFs can be accounted for by moisture and volatile matter content of coal in residential combustion.