Abstract. Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize chemical components of brown carbon (BrC), yet the molecular basics and formation mechanisms of chromophores decomposed by parallel factor (PARAFAC) analysis are not fully understood. Here, water-soluble organic carbon (WSOC) in aerosols from Karachi, Pakistan, were characterized with EEM spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Three PARAFAC components were identified, including two humic-like (C1 and C2), and one protein-like (C3) species. Among them, the C2 shows the longest emission maxima (~494 nm), and correlates tightly with the mass absorption efficiency at 365 nm (MAE365), the character of BrC. Molecular families associated with each of the three components were determined by Spearman correlation analysis between FT-ICR MS peaks and PARAFAC component intensities. The C1 and C2 components are associated with nitrogen-enriched compounds, despite that C2 more with higher aromaticity, higher N content, and highly oxygenated compounds. The formulas associated with C3 include fewer nitrogen-containing species, with a lower unsaturated degree and oxidation state. A dominant oxidation pathway for the formation of C1 and C2 components was suggested, notwithstanding their different precursor types. A large number of formulas associated with C2 were found to be located in the “potential BrC” region, overlapped with BrC-associated formulas, and readily correlated tightly with MAE365. This suggests that the compounds illuminating C2 may have also contributed substantially to the BrC light absorption. These findings were important for future studies using the EEM-PARAFAC method to explore the compositions, processes, and sources of atmospheric BrC.
Abstract The Asia‐Pacific Economic Cooperation (APEC) summit took place in Beijing, China, 5–11 November 2014, during which numerous measures were performed to control the air pollution, and consequently, the sky of Beijing was so clean that the public called it “APEC blue.” The concentrations before, during, and after the APEC summit are 14.4 ± 6.81 µg C/m 3 , 6.66 ± 2.99 µg C/m 3 , and 32.3 ± 10.6 µg C/m 3 , respectively, for organic carbon (OC), and 2.27 ± 1.17 µg C/m 3 , 0.76 ± 0.52 µg C/m 3 , and 4.99 ± 1.74 µg C/m 3 , respectively, for elemental carbon (EC). We quantify the contributions of fossil and nonfossil sources to the OC and EC using radiocarbon. Results show that the contribution of nonfossil sources is 56 ± 1% (before APEC), 61 ± 1% (during APEC), and 48 ± 1% (after APEC), respectively, for OC, and 36 ± 4% (before APEC), 46 ± 1% (during APEC), and 33 ± 4% (after APEC), respectively, for EC. Comparing to the period before APEC, 70% and 60% of fossil EC and OC and 60% and 50% of nonfossil EC and OC are reduced, respectively, implying that the control on the nonfossil sources has considerable contribution to the good air quality in Beijing. Both EC and OC mass loadings during the APEC summit would have increased by 60% if the biomass‐burning activities were not taken into account for control. In such a case, the atmospheric visibility would decrease 20% at least and the blue sky thereby would likely not have been visible during the summit.
Abstract The Green Revolution (GR) enhances crop yields significantly that contributes greatly to the social and economic development of many less developed countries. However, the increasing crop yields might rise crop residue biomass burning, leading to adverse environmental and health consequences. We assess the impact of crop residue burning associated with the GR-induced growing crop yields on benzo[a]pyrene (BaP) pollution, a congener of polycyclic aromatic hydrocarbons with strong carcinogenicity. We find a significant increasing trend of BaP emission and contamination from crop residue biomass burning from the mid-1960s to 2010s in India, coinciding with the growing crop yields occurring during the GR. Our results reveal that agricultural BaP emission driven lifetime lung cancer risk (ILCR) in India increased 2.6 times from the onset of GR in the mid-1960s to 2014 and the 57% population in India was exposed to the BaP level higher than the India national standard (1 ng m −3 ). We show that the reduction of open crop residue burning during the rice and wheat residue burning period would be a very effective measure to reduce BaP environmental contamination and health risk.
Abstract. Organosulfur compounds (OrgSs), especially organosulfates, have been widely reported at large quantities in particulate organic matter found in various atmospheric environments. Despite various kinds of organosulfates and their formation mechanisms being previously identified, a large fraction of OrgSs remain unexplained at the molecular level, impeding further knowledge on additional formation pathways and critical environmental parameters that help to explain their concentrations. In this work, the abundance and molecular composition of OrgSs in fine particulate samples collected in Guangzhou was reported. Our results revealed that organic sulfur can averagely contribute to 30 % of total particulate sulfur, and showed positively correlations with the SO2 (r = 0.37, p < 0.05) and oxidants (NOx+O3, r = 0.40, p < 0.01). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results presented that more than 80 % by number of the detected OrgSs in our samples have the elemental composition of O/(4S+3N) ≥ 1, indicating that they were largely in the form of oxidized organosulfates and/or nitrooxy organosulfates. Many OrgSs, which are tentatively attributed to previously identified biogenic and anthropogenic origins, were also present in aerosols derived from freshly-emitted combustion sources. Results show that the formation of OrgSs through an epoxide intermediate pathway could be as much as 46 %, and the oxidants levels could explain 20 % variation of organic sulfur mass. The analysis from our large FT-ICR MS dataset suggests that relative humidity, oxidation of biogenic volatile organic compounds via ozonolysis, and NOx-related nitrooxy organosulfate formations were the major reasons for the molecular variation of OrgSs, possibly highlighting the importance of heterogeneous reactions involving either the uptake of SO2 or the heterogeneous oxidations of particulate organosulfates into additional unrecognized OrgSs.
The concentrations of eight organophosphate esters (OPEs) have been investigated in air, snow and seawater samples collected during the cruise of ARK-XXVIII/2 from sixth June to third July 2014 across the North Atlantic and the Arctic. The sum of gaseous and particle concentrations (ΣOPE) ranged from 35 to 343 pg/m3. The three chlorinated OPEs accounted for 88 ± 5% of the ΣOPE. The most abundant OPE was tris(2-chloroethyl) phosphate (TCEP), with concentrations ranging from 30 to 227 pg/m3, followed by three major OPEs, such as tris(1-chloro-2-propyl) phosphate (TCPP, 0.8 to 82 pg/m3), tri-n-butyl phosphate (TnBP, 2 to 19 pg/m3), and tri-iso-butyl phosphate (TiBP, 0.3 to 14 pg/m3). The ΣOPE concentrations in snow and seawater ranged from 4356 to 10561 pg/L and from 348 to 8396 pg/L, respectively. The atmospheric particle-bound dry depositions of TCEP ranged from 2 to 12 ng/m2/day. The air-seawater gas exchange fluxes were dominated by net volatilization from seawater to air for TCEP (mean, 146 ± 239 ng/m2/day), TCPP (mean, 1670 ± 3031 ng/m2/day), TiBP (mean, 537 ± 581 ng/m2/day) and TnBP (mean, 230 ± 254 ng/m2/day). This study highlighted that OPEs are subject to long-range transport via both air and seawater from the European continent and seas to the North Atlantic and the Arctic.
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