Comparison of acidity and chemical composition of summertime cloud water and aerosol at an alpine site in Northwest China: Implications for the neutral property of clouds in the free troposphere.

Aerosol and cloud acidity are essential to human health, ecosystem health and productivity, as well as climate effects. The main chemical composition of cloud water greatly varies in different regions, resulting in substantial differences in the pH of cloud water. However, the influences of the anthropogenic emissions of acidic gases and substances, alkaline dust components, and dicarboxylic acids (diacids) on the ground concerning the acidity of cloud water in the free troposphere of the Guanzhong Plain, China, remain clear. In this study, cloud water and PM2.5 samples were simultaneously collected in the troposphere (Mt. Hua, 2060 m a.s.l). The results indicated that the cloud water was alkaline (pH = 7.6) and PM2.5 was acidic (pH = 3.2). These results showed the neutral property of clouds collected in the heavily polluted Guanzhong Plain, although most previous studies always considered acidity as a marker of pollution. The sulfate (SO42-), nitrate (NO3-), and ammonium (NH4+) (SNA) of particulate matter and cloud water in the same period were compared. SO42- was dominant in particulate matters (accounting for 63.4 % of the total SNA) but substantially decreased in cloud water (only 30.1 % of the total SNA), whereas NO3- and NH4+ increased from 28.5 % and 8.2 % to 39.8 % and 30.2 %, respectively. This could be attributed to the complex formation mechanism and sources of SO42- and NO3- in the cloud. The results of ion balance indicated that a significant deficit of inorganic anion equivalents was observed in the cloud water samples. The high concentration of diacids in the cloud phase (1237.4 µg L-1) may facilitate the formation of salt complexes with NH4+, thus influencing the acidity of the cloud water. The pH of cloud water has increased in recent decades due to the sustained reduction of sulfur dioxide, which may also affect the acidity of future precipitation.

Comparison of chemical composition and acidity of size-resolved inorganic aerosols at the top and foot of Mt. Hua, Northwest China: The role of the gas-particle distribution of ammonia.

Aerosol pH is not only a diagnostic indicator of secondary aerosol formation, but also a key factor in the specific chemical reaction routes that produce sulfate and nitrate. To understand the characteristics of aerosol acidity in the Mt. Hua, the chemical fractions of water-soluble inorganic ions in the atmospheric PM2.5 and size-resolved particle at the top and foot of Mt. Hua in summer 2020 were studied. The results showed the mass concentrations of PM2.5 and water-soluble ions at the foot were 2.0-2.6 times higher than those at the top. The secondary inorganic ions, i.e., SO42-, NO3-, and NH4+ (SNA) were 56 %-61 % higher by day than by night. SO42- was mainly distributed in the fine particles (Dp < 2.1 µm). NO3- showed a unimodal size distribution (peaking at 0.7-1.1 µm) at the foot and a bimodal (0.7-1.1 µm and 4.7-5.8 µm) size distribution at the top. At the top site, the distribution of NO3- in coarse particles (> 2.1 µm) was mainly attributed to the gaseous HNO3 volatilized from fine particles reacting with cations in coarse particles to form non-volatile salts (such as Ca(NO3)2). The pH values of PM2.5 were 2.7 ± 1.3 and 3.3 ± 0.42 at the top and foot, respectively. NH4+/NH3(g) plays a decisive role in stabilizing aerosol acidity. In addition, the increase of the liquid water content (LWC) at the foot facilitates the gas-particle conversion of NH3, while the H+ concentration was diluted, resulting in a decrease in acidity at the foot. NH4+/NH3 had good linear correlations with SO42-, NO3-, and LWC during the daytime at both sites, indicating that SO42-, NO3-, and LWC together affect the gas-particle distribution of ammonia by day: however, the effect of LWC at night was not evident.

Comparison of Gas-Particle Partitioning of Glyoxal and Methylglyoxal in the Summertime Atmosphere at the Foot and Top of Mount Hua.

Glyoxal and methylglyoxal are important volatile organic compounds in the atmosphere. The gas-particle partitioning of these carbonyl compounds makes significant contributions to O3 formation. In this study, both the gas- and particle-phase glyoxal and methylglyoxal concentrations at the foot and top of Mount Hua were determined simultaneously. The results showed that the gaseous-phase glyoxal and methylglyoxal concentrations at the top were higher than those at the foot of the mountain. However, the concentrations for the particle phase showed the opposite trend. The average theoretical values of the gas-particle partitioning coefficients of the glyoxal and methylglyoxal concentrations (4.57 × 10-10 and 9.63 × 10-10 m3 µg-1, respectively) were lower than the observed values (3.79 × 10-3 and 6.79 × 10-3 m3 µg-1, respectively). The effective Henry's law constants (eff.KH) of the glyoxal and methylglyoxal were in the order of 108 to 109 mol/kgH2O/atm, and they were lower at the foot than they were at the top. The particle/gas ratios (P/G ratios) of the glyoxal and methylglyoxal were 0.039 and 0.055, respectively, indicating more glyoxal and methylglyoxal existed in the gas phase. The factors influencing the partitioning coefficients of the glyoxal and methylglyoxal were positively correlated with the relative humidity (RH) and negatively correlated with the PM2.5 value. Moreover, the partitioning coefficient of the glyoxal and methylglyoxal was more significant at the top than at the foot of Mount Hua.

Influence of vertical transport on chemical evolution of dicarboxylic acids and related secondary organic aerosol from surface emission to the top of Mount Hua, Northwest China.

Dicarboxylic acids are strong hygroscopic organic compounds in the atmosphere, and thus significantly affect the cloud formation process and radiative forcing on a regional scale. So far, the evolution of dicarboxylic acids during vertical transport from the surface to the mountaintop has yet to be explicitly understood. In this study, the molecular distribution and stable carbon isotopic (δ13C) compositions of dicarboxylic acids and related organic compounds (DCRCs) in PM2.5 were measured simultaneously at the top (c. 2060 m a.s.l.) and foot (c. 400 m a.s.l.) of Mount (Mt.) Hua during the summer of 2020. Due to the strong anthropogenic emissions at ground level, the concentrations of DCRCs at foot of Mt. Hua were generally higher than those at the top. Oxalic acid (C2) was the predominant diacid in both sites, whose concentrations at foot and top of Mt. Hua were 87-852 and 40-398 ng m-3, respectively. Ratios of adipic acid to azelaic acid (C6/C9), phthalic aid to azelaic acid (pH/C9), glyoxal to methylglyoxal (Gly/mGly), and lower δ13C values (-21.0 ± 2.3 ‰ and - 21.9 ± 2.7 ‰) of C2 indicated that the contributions of anthropogenic sources to DCRCs in PM2.5 in the mountain region are more significant than biogenic sources. Aerosols from the foot of Mt. Hua could affect the atmosphere on the top of the mountain via vertical transport under the influence of daytime valley wind, even though the altitude of Mt. Hua is beyond the boundary layer most of time. The value δ13C of C2 is linearly correlated with C2/mGly, C2/pyruvic acid (Pyr), C2/glyoxylic acid (ωC2) at the top of the mountain, and C2/Gly, C2/ωC2 at the foot of the mountain, indicating that the formation pathway of C2 is mGly-Pyr-ωC2-C2 at the top of Mt. Hua and Gly-ωC2-C2 at the foot of Mt. Hua.

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in wintertime aerosols of Northwest China.

Dicarboxylic acids are one of the important water-soluble organic compounds in atmospheric aerosols, causing adverse effects to both climate and human health. More attention has therefore been paid to organic acids in aerosols. In this study, the molecular distribution and diurnal variations of wintertime dicarboxylic acids in a rural site of Guanzhong Plain, Northwest China, were explored. Oxalic acid (C2, day: 438.9 ± 346.8 ng m-3, night: 398.8 ± 392.3 ng m-3) is the most abundant compound followed by methylglyoxal (mGly, day: 207.8 ± 281.1 ng m-3, night: 222.9 ± 231.0 ng m-3) and azelaic (C9, day: 212.8 ± 269.1 ng m-3, night: 211.4 ± 136.7 ng m-3) acid. The ratios of C9/C6 and C9/Ph indicating that atmospheric dicarboxylic acids in winter in the region mainly come from biomass burning. Furthermore, secondary inorganic ions (NO3-, SO42-, and NH4+), relative humidity, liquid water content, and in-situ pH of aerosols are highly linearly correlated with C2, suggesting that liquid phase oxidation is an important pathway for the formation of dicarboxylic acids. The δ13C analysis of C2 suggested that lighter carbon isotope compositions tend to be oxidized to form aqueous-phase secondary organic aerosols (aqSOA), leading to the decay of 13C in aqSOA products rather than aerosol aging. This study provides a theoretical basis for the mechanism of formation of dicarboxylic acid.

Spatial distribution of PM2.5-bound elements in eighteen cities over China: policy implication and health risk assessment.

In this study, 30 elements in fine particulate matter (PM2.5) were measured in 18 Chinese cities in 2013. Elemental pollution in northern, southwest, and central China were severe, attributing to excessive coal and biomass combustion in these regions. The concentrations of S, Cl, and K in these areas were 8.21 ± 3.90, 4.03 ± 1.96, and 1.59 ± 0.613 µg/m3, respectively, which were 1.6-2.7 times higher than those in other regions of China. In addition, the industrial emissions in northeast and north China were large, leading to the elevated heavy metal concentration of 1.32 ± 1.17 µg/m3, especially Zn, Pb, Cr, Cd, and Br. Soil dust was the highest in northwest China among the five regions with the concentration of crustal elements of 6.37 ± 4.51 µg/m3. Moreover, although the levels of elemental concentration in east and southeast China were relatively acceptable, regulators must pay attention to elevated level of V (0.009 ± 0.006 µg/m3) in these areas. Compared with 2003, several elements have deteriorated in some cities. For example, As increased by 70%, 18%, and 155% in Changchun, Beijing, and Jinchang, respectively. However, ~ 77% measured elements, e.g., Ti, Fe, and Pb markedly reduced in 2013, with reduction rates of 13-81%. These indicate that the government's policies related to particle-bound elements have shown certain positive environmental effects. For the health risks from the heavy metals in 2013, the non-cancer risks of As and Cd must not be neglected. The cancer risks of As and Pb were much higher than the international safety limit (10-4). More prominent health risks were found in southwest, central, and northwest China. Therefore, the government should accelerate the shift to cleaner energy in underdeveloped areas of China to obtain more environmental and health benefits.

Characterization and health risk assessment of airborne pollutants in commercial restaurants in northwestern China: Under a low ventilation condition in wintertime.

Impacts on indoor air quality of dining areas from cooking activities were investigated in eight categories of commercial restaurants including Szechwan Hotpot, Hunan, Shaanxi Noodle, Chinese Barbecue, Chinese Vegetarian, Korean Barbecue, Italian, and Indian, in Northwestern China during December 2011 to January 2012. Chemical characterization and health risk assessment for airborne carbonyls, and particulate-bound polycyclic aromatic hydrocarbons (PAHs) and heavy metals were conducted under low ventilation conditions in wintertime. The highest total quantified carbonyls (Σcarbonyls) concentration of 313.6µgm-3 was found in the Chinese Barbecue, followed by the Szechwan Hotpot (222.6µgm-3) and Indian (221.9µgm-3) restaurants. However, the highest Σcarbonyls per capita was found at the Indian restaurant (4500µgcapita-1), suggesting that cooking methods such as stir-fly and bake for spices ingredients released more carbonyls from thermal cooking processes. Formaldehyde, acetaldehyde, and acetone were the three most abundant species, totally accounting for >60% of mass concentrations of the Σcarbonyls. Phenanthrene, chrysene, and benzo[a]anthracene were the three most abundant PAHs. Low molecular weight fraction (ΣPAHs≤178) had the highest contributions accounting for 40.6%-65.7%, much greater than their heaver counterparts. Diagnostic PAHs ratios suggest that cooking fuel and environmental tobacco smoke (ETS) contribute to the indoor PAHs profiles. Lead was the most abundant heavy metal in all sampled restaurants. High quantity of nickel was also found in samples due to the emissions from stainless-steel made kitchen utensils and cookware and ETS. Cancer risk assessments on the toxic substances demonstrate that the working environment of dining areas were hazard to health. Formation of reactive organic species (ROS) from the cooking activities was evidenced by measurement of hydroxyl radical (OH) formed from simulating particulate matter (PM) react with surrogate lung fluid. The highest OH concentration of 294.4ngm-3 was detected in Chinese Barbecue. In addition, the elevation of the concentrations of PM and OH after non-dining periods implies that the significance of formation of oxidizing-active species indoor at poor ventilation environments.

Determination of picogram quantities of chlortoluron in soil samples by luminol-chitosan chemiluminescence system.

Based on the enhancing effect of chitosan (CS) on luminol-dissolved oxygen chemiluminescence (CL) reaction, a flow injection (FI) luminol-CS CL system was established. It was found that the increase of CL intensity was proportional to the concentrations of CS ranging from 0.7 to 10.0 µmol l(-1). In the presence of chlortoluron (CTU), the CL intensity of luminol-CS system could be obviously inhibited and the decrements of CL intensity were linearly proportional to the logarithm of CTU concentrations ranging from 0.01 to 70.0 ng ml(-1), giving the limit of detection 3.0 pg ml(-1) (3σ). At a flow rate of 2.0 ml min(-1), the whole process including sampling and washing could be accomplished within 36 s, offering a sample throughput of 100 h(-1). The proposed FI-CL method was successfully applied to the determination of CTU in soil samples with recoveries ranging from 95.0 % to 105.3 % and the relative standard deviations (RSDs) of less than 4.0 %.