Brown carbon (BrC) plays an essential impact on radiative forcing due to its ability to absorb sunlight. In this study, the optical properties and molecular characteristics of water-soluble and methanol-soluble organic carbon (OC; MSOC) emitted from the simulated combustion of biomass and coal fuels and vehicle emissions were investigated using ultraviolet–visible (UV–vis) spectroscopy, excitation–emission matrix (EEM) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with electrospray ionization (ESI). The results showed that these smoke aerosol samples from biomass burning (BB) and coal combustion (CC) had a higher mass absorption efficiency at 365 nm (MAE₃₆₅) than vehicle emission samples. A stronger MAE₃₆₅ value was also found in MSOC than water-soluble organic carbon (WSOC), indicating low polar compounds would possess a higher light absorption capacity. Parallel factor (PARAFAC) analysis identified six types of fluorophores (P1–6) in WSOC including two humic-like substances (HULIS-1) (P1 and P6), three protein-like substances (PLOM) (P2, P3, and P5), and one undefined substance (P4). HULIS-1 was mainly from aging vehicle exhaust particles; P2 was only abundant in BB aerosols; P3 was ubiquitous in all tested aerosols; P4 was abundant in fossil burning aerosols; and P5 was more intense in fresh vehicle exhaust particles. The MSOC chromophores (six components; C1–6) exhibited consistent characteristics with WSOC, suggesting the method could be used to indicate the origins of chromophores. FT-ICR mass spectra showed that CHO and CHON were the most abundant components of WSOC, but S-containing compounds appeared in a higher abundance in CC aerosols and vehicle emissions than BB aerosols, while considerably fewer S-containing compounds largely with CHO and CHON were detected in MSOC. The unique formulas of different sources in the van Krevelen (VK) diagram presented different molecular distributions. To be specific, BB aerosols with largely CHO and CHON had a medium H ∕ C and low O ∕ C ratio, while CC aerosols and vehicle emissions largely with S-containing compounds had an opposite H ∕ C and O ∕ C ratio. Moreover, the light absorption capacity of WSOC and MSOC was positively associated with the unsaturation degree and molecular weight in the source aerosols. The above results are potentially applicable to further studies on the EEM-based or molecular-characteristic-based source apportionment of chromophores in atmospheric aerosols.

Brown carbon (BrC) draws increasing attention due to its effects on climate and other environmental factors. In China, household coal burned for heating and cooking purposes releases huge amounts of carbonaceous particles every year; however, BrC emissions have rarely been estimated in a persuasive manner due to the unavailable emission characteristics. Here, seven coals jointly covering geological maturity from low to high were burned in four typical stoves as both chunk and briquette styles. The optical integrating sphere (IS) method was applied to measure the emission factors (EFs) of BrC and black carbon (BC) via an iterative process using the different spectral dependence of light absorption for BrC and BC and using humic acid sodium salt (HASS) and carbon black (CarB) as reference materials. The following results have been found: (i) the average EFs of BrC for anthracite coal chunks and briquettes are 1.08 ± 0.80 and 1.52 ± 0.16 g kg ⁻¹ , respectively, and those for bituminous coal chunks and briquettes are 8.59 ± 2.70 and 4.01 ± 2.19 g kg ⁻¹ , respectively, reflecting a more significant decline in BrC EFs for bituminous coals than for anthracites due to briquetting. (ii) The BrC EF peaks at the middle of coal's geological maturity, displaying a bell-shaped curve between EF and volatile matter ( V _daf ). (iii) The calculated BrC emissions from China's residential coal burning amounted to 592 Gg (1 Gg = 10 ⁹ g) in 2013, which is nearly half of China's total BC emissions. (iv) The absorption Ångström exponents (AAEs) of all coal briquettes are higher than those of coal chunks, indicating that the measure of coal briquetting increases the BrC ∕ BC emission ratio and thus offsets some of the climate cooling effect of briquetting. (v) In the scenario of current household coal burning in China, solar light absorption by BrC (350–850 nm in this study) accounts for more than a quarter (0.265) of the total absorption. This implies the significance of BrC to climate modeling.

Source apportionment of fine particles (PM_2.5) at a background site in North China in the winter of 2014 was done using statistical analysis, radiocarbon (¹⁴C) measurement and positive matrix factorization (PMF) modeling. Results showed that the concentration of PM_2.5 was 77.6 ± 59.3 µg m⁻³, of which sulfate (SO₄²⁻) concentration was the highest, followed by nitrate (NO₃⁻), organic carbon (OC), elemental carbon (EC) and ammonium (NH₄⁺). As demonstrated by backward trajectory, more than half of the air masses during the sampling period were from the Beijing–Tianjin–Hebei (BTH) region, followed by Mongolia and the Shandong Peninsula. Cluster analysis of chemical species suggested an obvious signal of biomass burning in the PM_2.5 from the Shandong Peninsula, while the PM_2.5 from the BTH region showed a vehicle emission pattern. This finding was further confirmed by the ¹⁴C measurement of OC and EC in two merged samples. The ¹⁴C result indicated that biogenic and biomass burning emission contributed 59 ± 4 and 52 ± 2 % to OC and EC concentrations, respectively, when air masses originated from the Shandong Peninsula, while the contributions fell to 46 ± 4 and 38 ± 1 %, respectively, when the prevailing wind changed and came from the BTH region. The minimum deviation between source apportionment results from PMF and ¹⁴C measurement was adopted as the optimal choice of the model exercises. Here, two minor overestimates with the same range (3 %) implied that the PMF result provided a reasonable source apportionment of the regional PM_2.5 in this study. Based on the PMF modeling, eight sources were identified; of these, coal combustion, biomass burning and vehicle emission were the main contributors of PM_2.5, accounting for 29.6, 19.3 and 15.9 %, respectively. Compared with overall source apportionment, the contributions of vehicle emission, mineral dust, coal combustion and biomass burning increased when air masses came from the BTH region, Mongolia and the Shandong Peninsula, respectively. Since coal combustion and vehicle emission have been considered as the leading emission sources to be controlled for improving air quality, biomass burning was highlighted in the present study.

Shipping emissions have significant influence on atmospheric environment as well as human health, especially in coastal areas and the harbour districts. However, the contribution of shipping emissions on the environment in China still need to be clarified especially based on measurement data, with the large number ownership of vessels and the rapid developments of ports, international trade and shipbuilding industry. Pollutants in the gaseous phase (carbon monoxide, sulfur dioxide, nitrogen oxides, total volatile organic compounds) and particle phase (particulate matter, organic carbon, elemental carbon, sulfates, nitrate, ammonia, metals) in the exhaust from three different diesel-engine-powered offshore vessels in China (350, 600 and 1600 kW) were measured in this study. Concentrations, fuel-based and power-based emission factors for various operating modes as well as the impact of engine speed on emissions were determined. Observed concentrations and emission factors for carbon monoxide, nitrogen oxides, total volatile organic compounds, and particulate matter were higher for the low-engine-power vessel (HH) than for the two higher-engine-power vessels (XYH and DFH); for instance, HH had NO_x EF (emission factor) of 25.8 g kWh⁻¹ compared to 7.14 and 6.97 g kWh⁻¹ of DFH, and XYH, and PM EF of 2.09 g kWh⁻¹ compared to 0.14 and 0.04 g kWh⁻¹ of DFH, and XYH. Average emission factors for all pollutants except sulfur dioxide in the low-engine-power engineering vessel (HH) were significantly higher than that of the previous studies (such as 30.2 g kg⁻¹ fuel of CO EF compared to 2.17 to 19.5 g kg⁻¹ fuel in previous studies, 115 g kg⁻¹ fuel of NO_x EF compared to 22.3 to 87 g kg⁻¹ fuel in previous studies and 9.40 g kg⁻¹ fuel of PM EF compared to 1.2 to 7.6 g kg⁻¹ fuel in previous studies), while for the two higher-engine-power vessels (DFH and XYH), most of the average emission factors for pollutants were comparable to the results of the previous studies, engine type was one of the most important influence factors for the differences. Emission factors for all three vessels were significantly different during different operating modes. Organic carbon and elemental carbon were the main components of particulate matter, while water-soluble ions and elements were present in trace amounts. The test inland ships and some test offshore vessels in China always had higher EFs for CO, NO_x, and PM than previous studies. Besides, due to the significant influence of engine type on shipping emissions and that no accurate local EFs could be used in inventory calculation, much more measurement data for different vessels in China are still in urgent need. Best-fit engine speeds during actual operation should be based on both emission factors and economic costs.

With the rapid growth in the number of both non-road and on-road diesel vehicles, the adverse effects of particulate matter (PM) and its constituents on air quality and human health have attracted increasing attentions. However, studies on the characteristics of PM and its composition emitted from diesel vehicles are still scarce, especially under real-world driving conditions. In this study, six excavators and five trucks that provided a wide range of emission standards and operation modes were tested, and PM emissions and their constituents – including organic carbon (OC), elemental carbon (EC), water-soluble ions (WSIs), elements, and organic species like polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and hopanes – as well as steranes were analyzed and characterized. The average emission factors for PM (EF_PM) from excavator and truck emissions were 829 ± 806 and 498 ± 234 mg kg⁻¹ fuel, respectively. EF_PM and PM constituents were significantly affected by fuel quality, operational mode, and emission standards. A significant correlation (R² = 0. 79, p < 0. 01) was found between EF_PM for excavators and the sulfur contents in fuel. The highest average EF_PM for working excavators was 904 ± 979 mg kg⁻¹ fuel as a higher engine load required in this mode. From pre-stage 1 to stage 2, the average EF_PM for excavators decreased by 58 %. For trucks, the average non-highway EF_PM at 548 ± 311 mg kg⁻¹ fuel was higher than the highway EF_PM at 497 ± 231 mg kg⁻¹ fuel. Moreover, the reduction rates were 63.5 and 65.6 % when switched from China II and III to China IV standards, respectively. Generally, the PM composition emitted from excavators was dominated by OC (39. 2 ± 21. 0 %) and EC (33. 3 ± 25. 9 %); PM from trucks was dominated by EC (26. 9 ± 20. 8 %), OC (9. 89 ± 12 %), and WSIs (4. 67 ± 5. 74 %). The average OC ∕ EC ratios for idling and working excavators were 3 to 4 times higher than those for moving excavators. Although the EF_PM for excavators and trucks was reduced with the constraint of regulations, the element fractions for excavators increased from 0.49 % in pre-stage 1 to 3.03 % in stage 2, and the fraction of WSIs for the China IV truck was 5 times higher than the average value of all other-level trucks. Furthermore, as compared with other diesel vehicles, wide ranges were found for excavators of the ratios of benzo[a]anthracene ∕ (benzo[a]anthracene + chrysene) (0.26–0.86), indeno[1,2,3-cd]pyrene ∕ (indeno[1,2,3-cd]pyrene + benzo[ghi]perylene) (0.20–1.0), and fluoranthene ∕ (fluoranthene + pyrene) (0.24–0.87), which might be a result of the complex characteristics of the excavator operation modes. A comparison of our results with those in the literature revealed that on-board measurement data more accurately reflect actual conditions. Although the fractions of the 16 priority PAHs in PM from the excavator and truck emissions were similar, the equivalent concentrations of total benzo[a]pyrene of excavators were 31 times than that for trucks, implying that more attention should be paid to non-road vehicle emissions.