Atmospheric Humic-like Substances Research Articles

Compositional and optical characteristics of aqueous brown carbon and HULIS in the eastern Indo-Gangetic Plain using a coupled EEM PARAFAC, FT-IR and 1H NMR approach

This study provides insights into the fluorophoric composition of aqueous brown carbon (BrCaq) and chemically-separated humic-like substances (HULIS): neutral HULIS (HULIS-n; at pH = 7) and acidic HULIS (HULIS-a; at pH = 2) on a seasonal and day-night basis in the eastern Indo-Gangetic Plain (IGP), India. A coupled approach including excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) model, Fourier-transformed infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to understand the links between structural, compositional and fluorophoric characteristics of BrCaq and HULIS fractions. HULIS fluorophores (HULISfluoro) with varying oxidation states transported from the northwest IGP were dominant during biomass burning seasons (post-monsoon and winter), while protein-like fluorophores (PRLISfluoro) from marine emissions showed large contributions during summer. HULIS-n moieties were mostly primary in nature with higher conjugation, while HULIS-a were associated with secondarily formed and aged species with a larger contribution from degradation products. A substantial presence of tyrosine-like proteins in both chemically-separated HULIS fractions indicated that atmospheric HULIS is not entirely humic or fulvic-like in the eastern IGP. Finally, the dominance of H-C-O groups across seasons suggested consistent fossil fuel signatures along with season-specific influence of photodegradable cellulose from marine organisms in the summer and biomass burning in the post-monsoon and winter.

Effects of aerosol water content and acidity on the light absorption of atmospheric humic-like substances in winter

Atmospheric humic-like substances (HULIS) could affect regional climate due to their strong light-absorbing capacity. Daily fine particulate matter (PM2.5) samples were collected from December 18, 2016 to January 8, 2017 at an urban site in Chongqing, Southwest China. The mean concentration of HULIS in terms of carbon (HULIS-C) was 6.4 ± 3.4 μg m−3, accounting for 72% of water-soluble organic carbon. The mass absorption efficiency at 365 nm (MAE365) and absorption Ångström index (AAE) of atmospheric HULIS were 2.8 ± 0.30 m2 g−1 C and 4.6 ± 0.37, respectively. Good correlations between the light absorption coefficients of HULIS at 365 nm (Abs365) and the concentrations of K+, elemental carbon, NO3−, and NH4+ were observed, with correlation coefficients higher than 0.83, indicating that biomass burning and secondary formation were potential sources of light-absorbing HULIS, as evidenced by abundant fluorescent components related to less-oxygenated HULIS. Comparing the changes in Abs365 values, concentrations of major water-soluble inorganic ions and carbonaceous compounds in PM2.5, and environmental factors during the clean and pollution periods, we found that extensive biomass burning during the pollution period contributed significantly to the increase of Abs365 values. Moreover, the aerosol pH during the pollution period was close to 4, and NO2 concentration and aerosol water content were about 1.6 and 2.7 times higher than those during the clean period, respectively, which were favorable to form secondary HULIS through aqueous phase reactions in the presence of high NOx, resulting in an evident increase in its light absorption. Knowledge generated from this study is critical for evaluating the regional radiative forcing of brown carbon in southwest China.

Formation of nitrogen-containing gas phase products from the heterogeneous (photo)reaction of NO2 with gallic acid

Heterogeneous reaction of gas phase NO2 with atmospheric humic-like substances (HULIS) is potentially an important source of volatile organic compounds (VOCs) including nitrogen (N)-containing compounds, a class of brown carbon of emerging importance. However, the role of ubiquitous water-soluble aerosol components in this multiphase chemistry, namely nitrate and iron ions, remains largely unexplored. Here, we used secondary electrospray ionization ultrahigh-resolution mass spectrometry for real-time measurements of VOCs formed during the heterogeneous reaction of gas phase NO2 with a solution containing gallic acid (GA) as a proxy of HULIS at pH 5 relevant for moderately acidic aerosol particles. Results showed that the number of detected N-containing organic compounds largely increased from 4 during the NO2 reaction with GA in the absence of nitrate and iron ions to 55 in the presence of nitrate and iron ions. The N-containing compounds have reduced nitrogen functional groups, namely amines, imines and imides. These results suggest that the number of N-containing compounds is significantly higher in deliquescent aerosol particles due to the influence of relatively higher ionic strength from nitrate ions and complexation/redox reactivity of iron cations compared to that in the dilute aqueous phase representative of cloud, fog, and rain water.

Atmospheric humic-like substances (HULIS) in Chongqing, Southwest China: Abundance, light absorption properties, and potential sources

Atmospheric humic-like substances (HULIS) have a great impact on radiative forcing and atmospheric oxidative capacity due to their efficient light absorption properties. Knowledge on atmospheric HULIS abundance and light absorption properties in southwest China is still very limited. In this study, a total of 81 daily samples of fine particulate matter (PM2.5) were collected at two sites in Chongqing during four one-month periods in 2015, each of which representing a typical season. Mass concentrations of HULIS in term of carbon (HULIS-C) were measured by a total organic carbon analyzer, while mass absorption efficiency at 365 nm (MAE365) and absorption Ångström exponent (AAE) were estimated from light absorption of HULIS that was recorded by UV–visible spectrophotometry. The annual mean concentration of HULIS-C was around 3.4 ± 1.6 μg m−3, while the annual mean values of MAE365 and AAE were approximately 2.7 ± 0.7 m2 g−1C and 4.0 ± 0.2, respectively. Seasonal variations were significant for MAE365 but negligible for AAE at both sites. A direct comparison of MAE365 of HULIS in this study with the median MAE365 values from different sources in laboratory studies indicated that crop residues burning and/or wood burning were the primary sources of light-absorbing HULIS, as is also supported by the strong correlation between the light absorption coefficient at 365 nm (Abs365) and K+ (r > 0.85, p < 0.01) throughout the year. Furthermore, the good correlation between Abs365 and secondary organic carbon implied secondary sources also contributed to light-absorbing HULIS (e.g., nitrated aromatic compounds production), as evidenced by the good correlation between Abs365 and NO3− and NH4+. The contribution of primary and secondary sources to light-absorbing HULIS was quantified using a machine learning algorithm, which showed >65% contribution from primary sources during the cold season, but only 35% during the warm seasons.

Impact of fossil and non-fossil fuel sources on the molecular compositions of water-soluble humic-like substances in PM2.5 at a suburban site of Yangtze River Delta, China

Abstract. Atmospheric humic-like substances (HULIS) affect the global radiation balance due to their strong light absorption at the ultraviolet wavelength. The potential sources and molecular compositions of water-soluble HULIS at a suburban site in the Yangtze River Delta from 2017 to 2018 were discussed, based on the results of the radiocarbon (14C) analysis and combining the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) technique in this study. The 14C results showed that the averaged non-fossil-fuel source contributions to HULIS were 39 ± 8 % and 36 ± 6 % in summer and winter, respectively, indicating significant contributions from fossil fuel sources to HULIS. The Van Krevelen diagrams obtained from the FT-ICR-MS results showed that the proportions of tannin-like and carbohydrate-like groups were higher in summer, suggesting significant contribution of HULIS from biogenic secondary organic aerosols (SOAs). The higher proportions of condensed aromatic structures in winter suggested increasing anthropogenic emissions. Molecular composition analysis on the CHO, CHON, CHOS, and CHONS subgroups showed relatively higher intensities of high O-containing macromolecular oligomers in the CHO compounds in summer, further indicating stronger biogenic SOA formation in summer. High-intensity phenolic substances and flavonoids, which were related to biomass burning and polycyclic aromatic hydrocarbon (PAH) derivatives indicating fossil fuel combustion emissions, were found in winter CHO compounds. Besides, two high-intensity CHO compounds containing condensed aromatic ring structures (C9H6O7 and C10H5O8) identified in the summer and winter samples were similar to those from off-road engine samples, indicating that traffic emissions were one of the important fossil fuel sources of HULIS at the study site. The CHON compounds were mainly composed of nitro compounds or organonitrates with significantly higher intensities in winter, which were associated with biomass burning emissions, in addition to the enhanced formation of organonitrates due to high NOx in winter. However, the high-intensity CHON molecular formulas in summer were referring to N-heterocyclic aromatic compounds, which were produced from the atmospheric secondary processes involving reduced N species (e.g., ammonium). The S-containing compounds were mainly composed of organosulfates (OSs) derived from biogenic precursors, namely long-chain alkane and aromatic hydrocarbon, which illustrate the mixed sources of HULIS. Generally, different policies need to be considered for each season due to the different seasonal sources (i.e., biogenic emissions in summer and biomass burning in winter for non-fossil-fuel sources, traffic emissions and anthropogenic SOA formation in both seasons, and additional coal combustion in winter). Measures to control emissions from motor vehicles and industrial processes need to be considered in summer. Additional control measures on coal power plants and biomass burning should be applied in winter. These findings add to our understanding of the interaction between the sources and the molecular compositions of atmospheric HULIS.

Significant Promotion of Light Absorption Ability and Formation of Triplet Organics and Reactive Oxygen Species in Atmospheric HULIS by Fe(III) Ions.

Metal ions are key components in atmosphere that potentially affect the optical properties and photochemical reactivity of atmospheric humic-like substances (HULIS), while this mechanism is still unclear. In this study, we demonstrated that atmospheric HULIS coupled with Fe3+, Cu2+, Zn2+, and Al3+ exhibited distinct optical properties and reactive intermediates from that of HULIS utilizing three-dimensional fluorescence spectroscopy and electron paramagnetic resonance spectroscopy. The HULIS components showed light absorption that increased by 56% for the HULIS-Fe3+ system, fluorescence blue shift, and fluorescence quenching, showing a certain dose-effect relationship. These are mainly attributed to the fact that the highly oxidative HULIS chromophores have a stronger complexing ability with Fe3+ ions than the other metal ions. In addition, triplet organics (promoting ratio: 53%) and reactive oxygen species (promoting ratio: 82.6%) in the HULIS-Fe3+ system showed obvious generation promotion. Therefore, the main assumption of the photochemical mechanisms of atmospheric HULIS in the HULIS-Fe3+ system is that Fe3+ ions can form 3HULIS*-Fe3+ complexation with photoexcited 3HULIS* and then transition to the ground state through energy transfer, electron transfer, or nonradiative transition, accompanied by the formation of singlet oxygen and hydroxyl radicals. Our results provide references for evaluating the radiative forcing and aging effect of metal ions on atmospheric aerosols.

Effects of Chemical Reactions on the Oxidative Potential of Humic Acid, a Model Compound of Atmospheric Humic-like Substances

Atmospheric particulate matter (PM) contains various chemicals, some of which generate in vivo reactive oxygen species (ROS). Owing to their high reactivity and oxidation ability, ROS can cause various diseases. To understand how atmospheric PM affects human health, we must clarify the PM components having oxidative potential (OP) leading to ROS production. According to previous studies, OP is exhibited by humic-like substances (HULIS) in atmospheric PM. However, the OP-dependence of the chemical structures of HULIS has not been clarified. Therefore, in this study, humic acid (HA, a model HULIS material) was exposed to ozone and ultraviolet (UV) irradiation, and its OP and structures were evaluated before and after the reactions using dithiothreitol (DTT) assay and Fourier transform infrared (FT-IR), respectively. The OP of HA was more significantly increased by UV irradiation than by ozone exposure. FT-IR analysis showed an increased intensity of the C=O peak in the HA structure after UV irradiation, suggesting that the OP of HA was increased by a chemical change to a more quinone-like structure after irradiation.

Molecular characterization of nitrogen-containing organic compounds in fractionated atmospheric humic-like substances (HULIS) and its relationship with optical properties

Diverse nitrogen-containing organics are important components of humic-like substances (HULIS) in the atmosphere. In this study, organic components in particulate matter (PM) samples representing multiple sources were separated by successive solvent fractionation, which were then analyzed by mass spectrometric and optical instruments. The CHON compounds were eluted and clustered into the Low-polar, Medium-polar, and High-polar fractions, and discrepancies of the polar-fractions were particularly reflected by molecular descriptors such as aromaticity, oxygen content and molecular weight. In addition, the results from the light-absorbing parameters (i.e., MAE365 and SUVA254) underscored the importance of the Low-polar and High-polar fractions on optical absorption properties. The Low-polar fraction accounted for 40% of the cumulative SUVA254 values, suggesting significant content of ultraviolet-absorbing organics. The High-polar fraction contributed 52% of the cumulative MAE365 values, indicating abundant light absorption capacity and efficiency. Significant improvements were made on statistical analysis of multidimensional data by a combination of the molecular descriptors and optical parameters. Molecular structures, including condensed aromatic, lignin-like, and aliphatic compounds observed in distinct electrospray ionization modes, were found as main contributors to the light absorption capacity and the abundances of fluorophores in individual polar-fractions. Differential contributions of molecular characteristics on types and abundances of fluorophores were further found among the samples of multiple sources. Conclusions obtained from this successive solvent fractionation experiment could promote development of the pretreatment method for exploring the potential light-absorbing organics, which also provide insights into the emission sources of organics that are related to specific light absorption and fluorescence properties.

Seasonal variability of nitroaromatic compounds in ambient aerosols: Mass size distribution, possible sources and contribution to water-soluble brown carbon light absorption

Nitroaromatic compounds (NACs) as important constituents of atmospheric humic-like substances (HULIS) and brown carbon (BrC) affect the Earth's climate and pose a serious environmental hazard. We investigated seasonal size-segregated NACs in aerosol samples from the urban background environment in Ljubljana, Slovenia. Total concentrations of twenty NACs in PM15.6 were on average from 0.51 ng m−3 (summer) to 109 ng m−3 (winter), and contributed the most to submicron aerosols (more than 74%). Besides 4-nitrocatechol (4NC) as the prevailing species, methylnitrocatechols (MNCs) and nitrophenols (NPs), we reported on some very rarely mentioned, but also on five novel NACs (i.e., 3H4NBA: 3-hydroxy-4-nitrobenzoic acid, 3MeO4NP: 3-methoxy-4-nitrophenol, 4Et5NC: 4-ethyl-5-nitrocatechol, 3Et5NC: 3-ethyl-5-nitrocatechol and 3MeO5NC: 3-methoxy-5-nitrocatechol). Concentrations of 3MeO5NC, 4Et5NC and 3Et5NC were enhanced during cold seasons, contributing up to 11% to total NAC in winter. In cold season, NAC size distributions were characterized with the peaks in the broader size range of 0.305–1.01 μm (accumulation mode), with 4NC and alkyl-nitrocatechols (∑(M/Et)NC) as the most abundant, followed by 4-nitrosyringol, nitrophenols and nitroguaiacols. In spring, a pronounced peak of ∑(M/Et)NC was observed in the accumulation mode (0.305–0.56 μm) as well as in the coarse one. A strong correlation of all NACs with ∑(M/Et)NC and levoglucosan indicates that primary emissions of wood burning were the most important source of NACs, but their secondary formation (e.g., aqueous-phase at higher ambient RH) in cold season could also be a significant one. In warmer season, NACs may be mostly derived from traffic-related aromatic VOCs. The contribution of NACs to the light absorption of the aqueous extracts was up to 10-times higher (contribution to Abs365 up to 31%) than their mass contributions to WSOC (up to 3%) of corresponding size-segregated aerosols, confirming that most of the identified NACs are strong BrC chromophores.

Humic-like substances (HULIS) in springtime aerosols at a high-altitude background station in the western North Pacific: Source attribution, abundance, and light-absorption

Atmospheric humic-like substances (HULIS) are important components of biomass-burning (BB) emissions and highly associated with light-absorbing organic aerosols (often referred to as brown carbon). This study highlights the importance of BB-emitted HULIS aerosols in peninsular Southeast Asian outflow to the subtropical western North Pacific. We determined various key light-absorbing characteristics of HULIS i.e. mass absorption cross-section (MACHULIS), absorbing component of the refractive index (kHULIS), and absorption Ångström exponent (AAEHULIS) based on ground-based aerosol light absorption measurements along with HULIS concentrations in springtime aerosols at Lulin Atmospheric Background Station (LABS; 2862 m above mean sea level), which is a representative high-altitude remote site in the western North Pacific. Daily variations of HULIS (0.58–12.92 μg m−3) at LABS were mostly linked with the influence from incoming air-masses, while correlations with BB tracers and secondary aerosols indicated the attribution of primary and secondary sources. Stronger light absorption capability of HULIS was clearly evident from MACHULIS and kHULIS values at 370 nm, which were about ~1.5 times higher during BB-dominated days (1.16 ± 0.75 m2 g−1 and 0.05 ± 0.03, respectively) than that during non-BB days (0.77 ± 0.89 m2 g−1 and 0.03 ± 0.04, respectively). Estimates from a simple radiative transfer model showed that HULIS absorption can add as much as 15.13 W g−1 to atmospheric warming, and ~46% more during BB-dominated than non-BB period, highlighting that HULIS light absorption may significantly affect the Earth–atmosphere system and tropospheric photochemistry over the western North Pacific.

Size-Segregated Atmospheric Humic-Like Substances (HULIS) in Shanghai: Abundance, Seasonal Variation, and Source Identification

Humic-like substances (HULIS) are of great interest due to their optical and chemical characteristics. In this study, a total of 180 samples of atmospheric particulate matter (PM) of different sizes were collected from summer 2018 to spring 2019, in order to analyze the size distribution, to investigate the seasonal variation and then to identify the key sources of HULIS. The annual mean concentration of HULIS in the total suspended particulates reached 5.12 ± 1.42 μg/m3. The HULIS concentration was extremely higher in winter (8.35 ± 2.06 μg/m3) than in autumn (4.88 ± 0.95 μg/m3), in summer (3.62 ± 1.68 μg/m3) and in spring (3.36 ± 0.99 μg/m3). The average annual ratio of water-soluble organic carbon (WSOC) to OC and the ratio of HULIS to WSOC reached 0.546 ± 0.092 and 0.56 ± 0.06, respectively. Throughout the whole year, the size distributions of WSOC and HULIS-C were relatively smooth. The peaks of WSOC appeared at 1.8~3.2 μm and 0.56~1.0 μm, while the peaks of HULIS-C were located at 3.2~5.6 μm, 1.0~1.8 μm and 0.18~0.32 μm. The distribution of the HULIS particle mode was similar in spring, summer and autumn, while there was a lower proportion of the coarse mode and a higher proportion of the condensation mode in winter. By using the comprehensive analysis of principal component analysis (PCA), air mass backward trajectories (AMBTs) and fire point maps, key sources of WSOC and HULIS in Shanghai were identified as biomass combustion (48.42%), coal combustion (17.49%), secondary formation (16.07%) and vehicle exhaust (5.37%). The remaining part might be contributed by crustal dust sources, marine sources and/or other possible sources. This study provides new insight into the characteristics and size distribution of HULIS in Shanghai, thereby providing a practical base for further modeling.

Effects of albumin, transferrin and humic-like substances on iron-mediated OH radical formation in human lung fluids

Inhalation of particulate matter is hypothesized to contribute to health effects by overproducing reactive oxygen species (ROS) and inducing oxidative stress. Fe(II) has been shown to contribute to ROS generation in acellular simulated lung fluids. Atmospheric humic-like substances (HULIS) have been shown to chelate Fe(II) and significantly enhance this ROS generation. Here, we investigate Fe(II)-mediated .OH generation from the iron active proteins in lung fluid, albumin and transferrin, and fulvic acid, a surrogate for HULIS, in human bronchoalveolar lavage fluid (BALF). We find that albumin enhances .OH generation from inorganic Fe(II) and that transferrin attenuates this enhancement. We estimate the rate constants for albumin-Fe(II) and fulvic acid-Fe(II) mediated O2.- reduction (1.9 ± 0.3) M−1 s−1 and (2.7 ± 0.3) M−1s−1 (pH = 5.5, T = 37 °C), 17–25 times the rate for free iron, which we measured to be (110 ± 20) × 10−3 M−1s−1, in agreement with the literature. .OH generation measured from fulvic acid-Fe(II) in BALF from 8 individuals with added fulvic acid is successfully predicted rates of .OH generation by mixtures of Fe(II), albumin, transferrin, fulvic acid, and ascorbate in saline solution. This indicates that fulvic acid enhances .OH formation in BALF, and that albumin and transferrin in BALF moderate the effect. We propose that fulvic acid, and thereby HULIS, is capable of mobilizing Fe(II) away from albumin and transferrin and this increases the formation rate of O2.- and ultimately of .OH. Furthermore, we find that albumin and transferrin have significantly different impacts on Fe(II)-mediated .OH than citrate, a common component of simulated lung fluids, a factor that should be considered carefully in the interpretation of results obtained from solutions containing citrate.

Nitrated monoaromatic hydrocarbons (nitrophenols, nitrocatechols, nitrosalicylic acids) in ambient air: levels, mass size distributions and inhalation bioaccessibility

Nitrated monoaromatic hydrocarbons (NMAHs) are ubiquitous in the environment and an important part of atmospheric humic-like substances (HULIS) and brown carbon. They are ecotoxic and with underresearched toxic potential for humans. NMAHs were determined in size-segregated ambient particulate matter collected at two urban sites in central Europe, Ostrava and Kladno, Czech Republic. The average sums of 12 NMAHs (Σ12NMAH) measured in winter PM10 samples from Ostrava and Kladno were 102 and 93 ng m−3, respectively, and 8.8 ng m−3 in summer PM10 samples from Ostrava. The concentrations in winter corresponded to 6.3–7.3% and 2.6–3.1% of HULIS-C and water-soluble organic carbon (WSOC), respectively. Nitrocatechols represented 67–93%, 61–73% and 28–96% of NMAHs in PM10 samples collected in winter and summer at Ostrava and in winter at Kladno, respectively. The mass size distribution of the targeted substance classes peaked in the submicrometre size fractions (PM1), often in the PM0.5 size fraction especially in summer. The bioaccessible fraction of NMAHs was determined by leaching PM3 samples in two simulated lung fluids, Gamble’s solution and artificial lysosomal fluid (ALF). More than half of NMAH mass is found bioaccessible, almost complete for nitrosalicylic acids. The bioaccessible fraction was generally higher when using ALF (mimics the chemical environment created by macrophage activity, pH 4.5) than Gamble’s solution (pH 7.4). Bioaccessibility may be negligible for lipophilic substances (i.e. log KOW > 4.5).

Effect of metal-organic interactions on the oxidative potential of mixtures of atmospheric humic-like substances and copper/manganese as investigated by the dithiothreitol assay

Excessive generation of reactive oxygen species (ROS) and the corresponding oxidative stress has been recognized as one important cause for the adverse health effects associated with exposure to ambient particulate matter (PM). Transition metals and humic-like substances (HULIS) in PM have been separately demonstrated to contribute to the oxidative potential (OP) of PM, however, only few studies investigated the impact of their interactions on the measured OP and the effect is little understood. HULIS is an abundant fraction of water-soluble organic material in PM and serves to represent real-world PM organics. In this study, we applied a cell-free dithiothreitol (DTT) assay to quantify the OP, termed as OPDTT, by two representative transition metals (i.e., copper (Cu) and manganese (Mn)), HULIS, and mixtures of HULIS and metals in concentration levels relevant to those in human lung fluid resulting from PM inhalation. The organic-metal mixture effect was found to be metal-specific and concentration-specific, covering the possibility spectrum from being synergistic, additive to antagonistic. HULIS was observed to suppress OPDTT up to 10–20% by Cu at a concentration of 0.08 μM while had no discernable effect at 0.5 μM Cu. On the contrary, obvious enhancement of OPDTT was recorded in the mixtures of HULIS and Mn (e.g. up to ~2 times at 2.5 μM of Mn) while no mixture effects could be discerned at 0.5 μM Mn. Our work demonstrates the need for considering the metal-organic interactions and the complexity when evaluating the total OP of their mixtures, such as ambient PM samples. Further work in metal-PM organics interactions should be conducted using methods capable of measuring specific oxidants, in addition to the ability to deplete the reducing agent (i.e., DTT), in order to acquire a deeper mechanistic insight into the interactions.

Humic-like substances global levels and extraction methods in aerosols

The abundance of humic-like substances in the atmosphere has received considerable attention since these substances play an important role in various atmospheric processes. The wide variety of quantitative techniques used to study humic-like substances produce dissimilar results, making data comparison difficult. Also, global background concentrations and the transfer of atmospheric humic-like substances are poorly known. Here, we compared resins to extract humic-like substances in aerosols, and we measured contents in aerosols from Mt. Fuji. Results show that diethylaminoethyl cellulose resins extracted more humic-like substances than the diethylaminoethyl resin (hydroxylated methacrylic polymer). The mean humic-like substances concentrations in the free troposphere in East Asia is similar to that in Europe, suggesting that the global background level of humic-like substances is 0.05 μg C m−3, based on the humic-like substances concentrations on Mt. Fuji and Mt. Sonnblick. Humic-like substances concentrations, especially fulvic acids concentration, at the summit of Mt. Fuji increased when air masses came from the continent along with the carbon monoxide and ozone.

Chemical characterization of laboratory-generated tar ball particles

Abstract. The chemical properties of laboratory-generated tar ball (Lab-TB) particles produced from dry distillate (wood tars) of three different wood species in the laboratory were investigated by analytical techniques that had never been used before for their characterization. The elemental compositions of laboratory-generated tar balls (Lab-TBs) from three tree species were very similar to one another and to those characteristic of atmospheric tar balls (TBs) collected from the savanna fire during the SAFARI 2000 sampling campaign. The O ∕ C and H ∕ C molar ratios of the generated Lab-TBs were at the upper limit characteristic of soot particles. The Fourier transform infrared spectroscopy (FT-IR) spectra of the generated Lab-TBs were very similar to one another as well and also showed some similarity with those of atmospheric humic-like substances (HULIS). The FT-IR measurements indicated that Lab-TBs have a higher proportion of aromatic structure than HULIS and the oxygen atoms of Lab-TBs are mainly found in hydroxyl and keto functional groups. Whereas Raman activity was detected in the starting materials of the Lab-TBs (wood tars) in the range of 1000–1800 cm−1, the Raman spectra of TBs were dominated by two pronounced bands with intensity maxima near 1580 (G band) and 1350 cm−1 (D band), indicating the presence of sp2-hybridized carbon structures and disorder in them, respectively. In the Py-GC-MS chromatograms of the Lab-TBs mostly aromatic compounds (aromatic hydrocarbons, oxygenated aromatics and heterocyclic aromatics) were identified in accordance with the results of Raman and FT-IR spectroscopy. According to organic carbon ∕ elemental carbon (OC ∕ EC) analysis using EUSAAR_2 thermal protocol, 22 % of the total carbon content of Lab-TBs was identified as EC, contrary to expectations based on the current understanding that negligible if any EC is present in this sub-fraction of the brown carbon family. Our results suggest that spherical atmospheric TBs with high C ∕ O molar ratios are closer to BC in many of their properties than to weakly absorbing HULIS.

Humic-Like Substances (HULIS) in Aerosols of Central Tibetan Plateau (Nam Co, 4730 m asl): Abundance, Light Absorption Properties, and Sources.

Humic-like substances (HULIS) are major components of light-absorbing brown carbon that play an important role in Earth's radiative balance. However, their concentration, optical properties, and sources are least understood over Tibetan Plateau (TP). In this study, the analysis of total suspended particulate (TSP) samples from central of TP (i.e., Nam Co) reveal that atmospheric HULIS are more abundant in summer than that in winter without obvious diurnal variations. The light absorption ability of HULIS in winter is 2-3 times higher than that in summer. In winter, HULIS are mainly derived from biomass burning emissions in South Asia by long-range transport. In contrast, the oxidation of anthropogenic and biogenic precursors from northeast part of India and southeast of TP are major sources of HULIS in summer.

Molecular characterization of primary humic-like substances in fine smoke particles by thermochemolysis–gas chromatography–mass spectrometry

In this study, the molecular structures of primary humic-like substances (HULIS) in fine smoke particles emitted from the combustion of biomass materials (including rice straw, corn straw, and pine branches) and coal, and atmospheric HULIS were determined by off-line tetramethylammonium hydroxide thermochemolysis coupled with gas chromatography and mass spectrometry (TMAH-GC/MS). A total of 89 pyrolysates were identified by the thermochemolysis of primary and atmospheric HULIS. The main groups were polysaccharide derivatives, N-containing compounds, lignin derivatives, aromatic acid methyl ester, aliphatic acid methyl ester, and diterpenoid derivatives. Both the type and distribution of pyrolysates among primary HULIS were comparable to those in atmospheric HULIS. This indicates that primary HULIS from combustion processes are important contributors to atmospheric HULIS. Some distinct differences were also observed. The aromatic compounds, including lignin derivatives and aromatic acid methyl ester, were the major pyrolysates (53.0%–84.9%) in all HULIS fractions, suggesting that primary HULIS significantly contributed aromatic structures to atmospheric HULIS. In addition, primary HULIS from biomass burning (BB) contained a relatively high abundance of lignin and polysaccharide derivatives, which is consistent with the large amounts of lignin and cellulose structures contained in biomass materials. Aliphatic acid methyl ester and benzyl methyl ether were prominent pyrolysates in atmospheric HULIS. Moreover, some molecular markers of specific sources were obtained from the thermochemolysis of primary and atmospheric HULIS. For example, polysaccharide derivatives, pyridine and pyrrole derivatives, and lignin derivatives can be used as tracers of fresh HULIS emitted from BB. Diterpenoid derivatives are important markers of HULIS from pine wood combustion sources. Finally, the differences in pyrolysate types and the distributions between primary and atmospheric HULIS suggested that the primary HULIS would undergo many atmospheric processes to reconstruct the macromolecular organic matter in atmospheric aerosols.

Volatility of mixed atmospheric humic-like substances and ammonium sulfate particles

Abstract. The volatility of organic aerosols remains poorly understood due to the complexity of speciation and multiphase processes. In this study, we extracted humic-like substances (HULIS) from four atmospheric aerosol samples collected at the SORPES station in Nanjing, eastern China, and investigated the volatility behavior of particles at different sizes using a Volatility Tandem Differential Mobility Analyzer (VTDMA). In spite of the large differences in particle mass concentrations, the extracted HULIS from the four samples all revealed very high-oxidation states (O : C &gt; 0.95), indicating secondary formation as the major source of HULIS in Yangtze River Delta (YRD). An overall low volatility was identified for the extracted HULIS, with the volume fraction remaining (VFR) higher than 55 % for all the regenerated HULIS particles at the temperature of 280 °C. A kinetic mass transfer model was applied to the thermodenuder (TD) data to interpret the observed evaporation pattern of HULIS, and to derive the mass fractions of semi-volatile (SVOC), low-volatility (LVOC) and extremely low-volatility components (ELVOC). The results showed that LVOC and ELVOC dominated (more than 80 %) the total volume of HULIS. Atomizing processes led to a size-dependent evaporation of regenerated HULIS particles, and resulted in more ELVOC in smaller particles. In order to understand the role of interaction between inorganic salts and atmospheric organic mixtures in the volatility of an organic aerosol, the evaporation of mixed samples of ammonium sulfate (AS) and HULIS was measured. The results showed a significant but nonlinear influence of ammonium sulfate on the volatility of HULIS. The estimated fraction of ELVOC in the organic part of the largest particles (145 nm) increased from 26 %, in pure HULIS samples, to 93 % in 1 : 3 (mass ratio of HULIS : AS) mixed samples, to 45 % in 2 : 2 mixed samples, and to 70 % in 3 : 1 mixed samples, suggesting that the interaction with ammonium sulfate tends to decrease the volatility of atmospheric organic compounds. Our results demonstrate that HULIS are important low-volatility, or even extremely low-volatility, compounds in the organic-aerosol phase. As important formation pathways of atmospheric HULIS, multiphase processes, including oxidation, oligomerization, polymerization and interaction with inorganic salts, are indicated to be important sources of low-volatility and extremely low-volatility species of organic aerosols.

Quantification of environmentally persistent free radicals and reactive oxygen species in atmospheric aerosol particles

Abstract. Fine particulate matter plays a central role in the adverse health effects of air pollution. Inhalation and deposition of aerosol particles in the respiratory tract can lead to the release of reactive oxygen species (ROS), which may cause oxidative stress. In this study, we have detected and quantified a wide range of particle-associated radicals using electron paramagnetic resonance (EPR) spectroscopy. Ambient particle samples were collected using a cascade impactor at a semi-urban site in central Europe, Mainz, Germany, in May–June 2015. Concentrations of environmentally persistent free radicals (EPFR), most likely semiquinone radicals, were found to be in the range of (1–7) × 1011 spins µg−1 for particles in the accumulation mode, whereas coarse particles with a diameter larger than 1 µm did not contain substantial amounts of EPFR. Using a spin trapping technique followed by deconvolution of EPR spectra, we have also characterized and quantified ROS, including OH, superoxide (O2−) and carbon- and oxygen-centered organic radicals, which were formed upon extraction of the particle samples in water. Total ROS amounts of (0.1–3) × 1011 spins µg−1 were released by submicron particle samples and the relative contributions of OH, O2−, C-centered and O-centered organic radicals were ∼ 11–31, ∼ 2–8, ∼ 41–72 and ∼ 0–25 %, respectively, depending on particle sizes. OH was the dominant species for coarse particles. Based on comparisons of the EPR spectra of ambient particulate matter with those of mixtures of organic hydroperoxides, quinones and iron ions followed by chemical analysis using liquid chromatography mass spectrometry (LC-MS), we suggest that the particle-associated ROS were formed by decomposition of organic hydroperoxides interacting with transition metal ions and quinones contained in atmospheric humic-like substances (HULIS).