Water Solubility Distribution of Organic Matter Accounts for the Discrepancy in Hygroscopicity among Sub- and Supersaturated Humidity Regimes.

Water uptake properties of organic matter (OM) are critical for aerosol direct and indirect effects. OM contains various chemical species that have a wide range of water solubility. However, the role of water solubility on water uptake by OM has poorly been investigated. We experimentally retrieved water solubility distributions of water-soluble OM (WSOM) from combustion of mosquito coil and tropical peat using the 1-octanol-water partitioning method. In addition, hygroscopic growth and cloud condensation nuclei (CCN) activity of solubility-segregated WSOM were measured. The dominant fraction of WSOM from mosquito coil smoldering was highly soluble (water solubility (S) > 10-2 g cm-3), while that from peat combustion contained ∼40% of less-soluble species (S < 10-3 g cm-3). The difference in water solubility distributions induced changes in the roles of less water-soluble fractions (S < 10-3 g cm-3) on CCN activity. Namely, the less water-soluble fraction from mosquito coil combustion fully dissolved at the point of critical supersaturation, while that for tropical peat smoldering was limited by water solubility. The present result suggests that water solubility distributions of OM, rather than its bulk chemical property, need to be quantified for understanding the water uptake process.

Distinctive Sources Govern Organic Aerosol Fractions with Different Degrees of Oxygenation in the Urban Atmosphere.

Understanding how the sources of an atmospheric organic aerosol (OA) govern its burden is crucial for assessing its impact on the environment and adopting proper control strategies. In this study, the sources of OA over Beijing were assessed year-around based on the combination of two separation approaches for OA, one from chemical fractionation into the high-polarity fraction of water-soluble organic matter (HP-WSOM), humic-like substances (HULIS), and water-insoluble organic matter (WISOM), and the other from statistical grouping using positive matrix factorization (PMF) of high-resolution aerosol mass spectra. Among the three OA fractions, HP-WSOM has the highest O/C ratio (1.36), followed by HULIS (0.56) and WISOM (0.17). The major sources of different OA fractions were distinct: HP-WSOM was dominated by more oxidized oxygenated OA (96%); HULIS by cooking-like OA (40%), less oxidized oxygenated OA (27%), and biomass burning OA (21%); and WISOM by fossil fuel OA (77%). In addition, our results provide evidence that mass spectral-based PMF factors are associated with specific substructures in molecules. These structures are further discussed in the context of the FT-IR results. This study presents an overall relationship of OA groups monitored by chemical and statistical approaches for the first time, providing insights for future source apportionment studies.

Polycyclic aromatic hydrocarbons in soils and lichen from the western Tibetan Plateau: Concentration profiles, distribution and its influencing factors.

The Tibetan Plateau (TP) is a huge area and rarely affected by human activity, and is regarded as one of the most remote regions on the earth. Many studies about the long-range atmospheric transport (LRAT) of semi-volatile organic compounds (SVOCs) were conducted in southern and central TP. However, there are very limited studies focused on PAHs in the western TP and the concentrations profiles, distribution and its controlling factors in this area remains unclear. Thus, to explore this knowledge gap, 37 surface soil samples and 23 lichen samples were collected and analyzed for PAHs. The total concentration of 16 US EPA's priority PAHs (∑16PAHs) in western TP ranges 14.4-59.5ng/g and 38.0-133ng/g dry weight (dw) with a mean value of 30.8 and 84.6ng/g dw in soil and lichen, respectively, which is lower than the concentrations in most remote areas worldwide. In the western TP, low molecular weight PAHs (2-3 rings) are dominant (occupied 77.4% and 87.9% on average in soil and lichen, respectively), implying a significant contribution of LRAT in this area. The significant linear correlations (R2 = 0.372-0.627, p < 0.05) between longitude and soil concentration suggest a strong impact of the westerly wind on the distribution of PAHs in soil. In addition, the concentration ratio of lichen/soil (L/S) was found to linearly increase with the increasing log KOA of individual PAH, suggesting lichen has a strong ability in filtering more lipophilic airborne pollutants in western TP.

Historical record of anthropogenic polycyclic aromatic hydrocarbons in a lake sediment from the southern Tibetan Plateau.

High-altitude lake sediments can be used as natural archives to reconstruct the history of pollutants. In this work, the temporal distribution of polycyclic aromatic hydrocarbons (PAHs) was determined in a sediment core collected from the southern Tibetan Plateau (TP), which was dated by using the 210Pb dating method and validated with the 137Cs fallout peak. The concentrations of the anthropogenic PAHs (Σ8PAH) in the sediment core ranged from 0.83 to 12 ng/g dw, and the fluxes of the Σ8PAH were in the range of 2.1-27 g/cm2/year. The temporal variations in the concentration and input flux of anthropogenic PAHs were low with little variability before the 1950s, and then gradually increased from the 1950s to the 1980s, and an accelerated increase was observed after the early 1980s. The content of total organic carbon played an insignificant role in affecting the time trends of PAHs in the sediment core. Diagnostic concentration fractions of PAH components indicate PAHs in the lake sediment of the southern TP which are mainly from biomass burning and/or from long-range atmospheric transport.

Abundance, chemical structure, and light absorption properties of humic-like substances (HULIS) and other organic fractions of forest aerosols in Hokkaido.

Atmospheric organic aerosol (OA) are considered as a significant contributor to the light absorption of OA, but its relationship with abundance, composition and sources are not understood well. In this study, the abundance, chemical structural characteristics, and light absorption property of HULIS and other low-to-high polar organics in PM0.95 collected in Tomakomai Experimental Forest (TOEF) were investigated with consideration of their possible sources. HULIS were the most abundant (51%), and correlation analysis revealed that biogenic secondary organic aerosols significantly contribute to HULIS. The mass spectra obtained using a high-resolution aerosol mass spectrometer (HR-AMS) showed that HULIS and highly polar water-soluble organic matter (HP-WSOM) were substantially oxygenated organic aerosol fractions, whereas water-insoluble organic matter (WISOM) had a low O/C ratio and more hydrocarbon-like structures. The WISOM fraction was the predominant light-absorbing organics. HULIS and WISOM showed a noticeable seasonal change in mass absorption efficiency (MAE365), which was highest in winter. Further, HULIS were shown to be less absorbing than those reported for urban sites. The findings in this study provide insights into the contribution of biogenic secondary OA on aerosol property and radiative forcing under varying contributions from other types of OA.

A national-scale characterization of organochlorine pesticides (OCPs) in intertidal sediment of China: Occurrence, fate and influential factors.

Organochlorine pesticides (OCPs) have been restricted for application for about 30 years in China. Intertidal zone is a sink for anthropogenic pollutants, and to better understand the current pollution status of OCPs in China, 324 surface sediment samples collected from 14 typical intertidal zones of China were analyzed for 22 OCPs. The total concentrations of OCPs ranged from 0.051 to 4141.711 ng/g, with DDTs and HCHs being the dominant components. Seasonal variations were not significant for most intertidal zones (p > 0.05), while significant spatial variations (p < 0.05) were found among 14 intertidal zones, with the highest OCPs concentrations detected in Jiulong Jiang (JLJ). The OCPs concentrations in intertidal sediments would rarely to frequently cause adverse biological effects and DDTs were the major threat. Apart from the historical usage of technical DDT and lindane, current usage of technical DDT and HCH were also implied, especially for intertidal zones such as Beidaihe (BDH) and Yingluo Wan (YLW). PCA analysis indicated that compounds within the same type of OCPs were from similar source, while different types of OCPs were generally from different sources and not used together. Our results further indicated that OCPs together with organic particles entered into the intertidal zones mainly through river input.