Characteristics of aerosol aminiums over a coastal city in North China: Insights from the divergent impacts of marine and terrestrial influences.

Aminium ions, as crucial alkaline components within fine atmospheric particles, have a notable influence on new particle formation and haze occurrence. Their concentrations within coastal atmosphere depict considerable variation due to the interplay of distinctive marine and terrestrial sources, further complicated by dynamic meteorological conditions. This study conducted a comprehensive examination of aminiums ions concentrations, with a particular focus on methylaminium (MMAH+), dimethylaminium (DMAH+), trimethylaminium (TMAH+), and triethylaminium (TEAH+) within PM2.5, over varying seasons (summer, autumn, and winter of 2019 and summer of 2021), at an urban site in the coastal megacity of Qingdao, Northern China. The investigations revealed that the total concentration of particulate aminium ions (∑Aminium) was 21.6 ± 23.6 ng/m3, exhibiting higher values in the autumn and winter compared to the two summer periods. Considering diurnal variations during autumn and winter, concentrations of particulate aminium ions (excluding TEAH+) exhibited a slight increase during the day compared to night, with a notable peak during the morning hours. However, it was not the case for TEAH+, which was argued to be readily oxidized by ambient oxidants in the afternoon. Additionally, the ∑Aminium within the summer demonstrated markedly elevated levels during the day compared to night, potentially attributed to daytime sea fog associated with sea-land breeze interactions. Positive matrix factorization results indicate terrestrial anthropogenic emissions, including vehicle emission mixed with road dust and primary pollution, as the primary sources of MMAH+ and DMAH+. Conversely, TMAH+ was predominantly emitted from agricultural and marine sources. With the dominance of sea breeze in summer, TMAH+ was identified as a primary marine emission correlated with sea salt, while MMAH+, DMAH+, and TEAH+ were postulated to undergo secondary formation. Furthermore, a notable inverse correlation was observed between TMAH+ and methanesulfonate in PM2.5, consistent with dynamic emissions of sulfur-content and nitrogen-content gases reported in the literature.

[Chemical Composition and Characterization of Nitroaromatic Compounds in Urban Areas of Shanghai].

The compositional characteristics, concentration of nitroaromatic compounds(NACs) in PM2.5 in urban Shanghai, and their correlation with gaseous precursors were investigated. A total of 39 winter and 46 summer PM2.5 samples from 2020 to 2021 were collected using a high-flow sampler and analyzed via ultra-performance liquid chromatography coupled with ESI-Orbitrap high-resolution mass spectrometry(UPLC-Orbitrap-HRMS). Quantitative analysis was performed on 12 NACs compounds, combined with backward trajectory meteorological elements, molecular composition, and classification analysis of CHON substances. The results showed that a total of 12 NACs had an average concentration in winter of 17.1 ng·m-3, which was three times higher than that in summer(5.7 ng·m-3), mainly due to air masses in winter coming primarily from the northern part of China with more biomass burning, whereas more air masses in summer came from the cleaner southeastern ocean. 4-Nitrophenol was the most abundant species of NACs in winter, whereas 4-nitrophenol(clean days) and 4-hydroxy-3-nitrobenzoic acid(polluted days) were the most abundant species in summer. Qualitative analysis based on features such as aromatic ring equivalence number(Xc), O/C, and H/C values for the identification and characterization of monocyclic and polycyclic aromatic compounds showed that CHON compounds were mainly aromatic compounds in winter and summer in urban Shanghai. The number and abundance of CHON compounds detected on PM2.5 polluted days were 2 and 1.5 times higher(winter) and 2.5 and 2 times higher(summer) than that on clean days, respectively. Comparing the analysis results of clean and polluted days in winter and summer, it was found that 80% of the CHON compounds with a relative abundance in the top 10 had O/N ≥ 3 and RDBE values between 5 and 8. The results suggest that these highly abundant CHON analogs may have had mononitro- or dinitro-substituted benzene rings. Correlation analysis between gaseous precursors and NACs indicated that oxidative reactive formation of VOCs(benzene, toluene, etc.) from anthropogenic emissions was the main source of NACs in summer. By contrast, it was influenced by a combination of biomass combustion emissions and secondary formation of oxidative NOx from anthropogenic VOCs in winter.

Underestimation of biomass burning contribution to PM2.5 due to its chemical degradation based on hourly measurements of organic tracers: A case study in the Yangtze River Delta (YRD) region, China.

Biomass burning (BB) has significant impacts on air quality and climate change, especially during harvest seasons. In previous studies, levoglucosan was frequently used for the calculation of BB contribution to PM2.5, however, the degradation of levoglucosan (Lev) could lead to large uncertainties. To quantify the influence of the degradation of Lev on the contribution of BB to PM2.5, PM2.5-bound biomass burning-derived markers were measured in Changzhou from November 2020 to March 2021 using the thermal desorption aerosol gas chromatography-mass spectrometry (TAG-GC/MS) system. Temporal variations of three anhydro-sugar BB tracers (e.g., levoglucosan, mannosan (Man), and galactosan (Gal)) were obtained. During the sampling period, the degradation level of air mass (x) was 0.13, indicating that ~87 % of levoglucosan had degraded before sampling in Changzhou. Without considering the degradation of levoglucosan in the atmosphere, the contribution of BB to OC were 7.8 %, 10.2 %, and 9.3 % in the clean period, BB period, and whole period, respectively, which were 2.4-2.6 times lower than those (20.8 %-25.9 %) considered levoglucosan degradation. This illustrated that the relative contribution of BB to OC could be underestimated (~14.9 %) without considering degradation of levoglucosan. Compared to the traditional method (i.e., only using K+ as BB tracer), organic tracers (Lev, Man, Gal) were put into the Positive Matrix Factorization (PMF) model in this study. With the addition of BB organic tracers and replaced K+ with K+BB (the water-soluble potassium produced by biomass burning), the overall contribution of BB to PM2.5 was enhanced by 3.2 % after accounting for levoglucosan degradation based on the PMF analysis. This study provides useful information to better understand the effect of biomass burning on the air quality in the Yangtze River Delta region.

[Characteristics of Nitroaromatic Compounds in PM2.5 in Urban Area of Shanghai].

Nitroaromatic compounds (NACs) are an important class of nitrogen-containing compounds in fine particles. The investigation of characteristics and seasonal variation of NACs in PM2.5 increases our knowledge about nitrogen-containing compounds and contributes to the scientific basis in formulating reduction policies of NOx in urban areas. In this study, we analyzed the chemical composition of PM2.5 samples collected from March 2018 to February 2019 in an urban location in Shanghai. A total of 2439-3695 organic molecular formulas were detected using UPLC-Orbitrap MS. Nine NACs were quantified using an internal standard method. In spring, ρ(NACs) ranged from 3.12 to 16.76 ng·m-3, and the average concentration was 9.31 ng·m-3. In summer, it ranged from 1.05 to 9.70 ng·m-3, and the average value was 4.16 ng·m-3. In autumn, it ranged from 2.87 to 36.27 ng·m-3, and its average was 9.84 ng·m-3. In winter, it ranged from 4.83 to 56.23 ng·m-3, and the average was 22.37 ng·m-3. 4-Nitrophenol accounted for more than 25% of the quantified NACs in different seasons. In summer, the concentration of 5-nitrosalicylic acid accounted for 36%, but it decreased to 19% in winter. NACs in summer mainly originated from secondary formation, as evidenced by their clear correlation with the oxidant level, whereas biomass burning became the main source of NACs in winter.

The development of a cell-based model for the assessment of carcinogenic potential upon long-term PM2.5 exposure.

To assess the carcinogenic potential of PM2.5 exposure, we developed a cell-based experimental protocol to examine the cell transformation activity of PM2.5 samples from different regions in China. The seasonal ambient PM2.5 samples were collected from three megacities, Beijing (BJ), Wuhan (WH), and Guangzhou (GZ), from November 2016 to October 2017. The mean concentrations of PM2.5 were much higher in the winter season (BJ: 109.64 µg/m3, WH: 79.99 µg/m3, GZ: 49.99 µg/m3) than that in summer season (BJ: 42.40 µg/m3, WH: 25.82 µg/m3, GZ: 19.82 µg/m3). The organic extracts (OE) of PM2.5 samples from combined summer (S) (June, July, August) or winter (W) (November, December, January) seasons were subjected to characterization of chemical components. We treated human bronchial epithelial (HBE) cells expressing CYP1A1 (HBE-1A1) with PM2.5 samples at doses ranging from 0 to 100 µg/mL (0, 1.563, 3.125, 6.25, 12.5, 25, 50, 100 µg/mL) and determined the phenotype of malignant cell transformation. A dose-response relationship was analyzed by benchmark dose (BMD) modeling, and the potential were indicated by BMDL10. The order of the carcinogenic risk of seasonal PM2.5 samples from high to low was BJ-W, WH-W, GZ-W, WH-S, BJ-S, and GZ-S. Notably, we found that the alteration in the lung cancer-related biomarkers, KRAS, PTEN, p53, c-Myc, PCNA, pAKT/AKT, and pERK/ERK was congruent with the activity of cell transformation and the content of specific components of polycyclic aromatic hydrocarbon (PAHs) bound to PM2.5. Taken together, we have successfully developed a cell-based alternative model for the evaluation of potent carcinogenicity upon long-term PM2.5 exposure.

Multiple organ injury in male C57BL/6J mice exposed to ambient particulate matter in a real-ambient PM exposure system in Shijiazhuang, China.

The development of a rodent ambient particulate matter (PM) inhalation system is critical for drawing causal inferences between PM exposure and the onset of human diseases. In this study, we constructed a real-ambient PM exposure system to investigate multi-organ injury and the reversibility of the impairments in C57BL/6 J male mice exposed to PM with a duration of up to three months in Shijiazhuang, a city with the highest PM2.5 concentration in China. This unique exposure system provided an optimal scenario for round-the-clock PM exposure absent a change in the physiochemical properties of PM and minimized the disturbance to the mice habitat. The mean concentration of PM2.5 in the exposure chambers was 89.95, 79.98, and 87.87 µg/m3 at three different time points, respectively: weeks 1-3, week 1-6, and week 1-12. The injury in multiple organs, including lung, brain, heart, testis, and intestine, was profound and was evident by the significant pathological and functional alterations. Pulmonary pathological examination revealed severe interstitial inflammatory and alveolar hemorrhage throughout the exposure, which was in line with the reduced lung function and the increased cytokine excretion in bronchoalveolar lavage fluid and blood plasma. Notably, the PM-mediated inflammatory response in different systems was correlated with the severity of the injury and the attenuation of pulmonary lesions in the recovery group. Thus, the PM2.5-induced inflammatory response, the chemical components-induced cytotoxicity, genetic damage, and oxidative stress might be implicated in the impairment of multiple murine organs. These findings revealed the severity, sensitivity, and reversibility of multi-organ injury in response to a real-ambient PM exposure.

An Integrated Source Apportionment Methodology and Its Application over the Yangtze River Delta Region, China.

An integrated source apportionment methodology is developed by amalgamating the receptor-oriented model (ROM) and source-oriented numerical simulations (SOM) together to eliminate the weaknesses of individual SA methods. This approach attempts to apportion and dissect the PM2.5 sources in the Yangtze River Delta region during winter. First, three ROM models (CMB, PMF, ME2) are applied and compared for the preliminary SA results, with information from PM2.5 sampling and lab analysis during the winter seasons. The detailed source category contribution of SOM to PM2.5 is further simulated using the WRF-CAMx model. The two pieces of information from both ROM and SOM are then stitched together to give a comprehensive information on the PM2.5 sources over the region. With the integrated approach, the detailed contributing sources of the ambient PM2.5 at different receptors including rural and urban, coastal and in-land, northern and southern receptors are analyzed. The results are compared with previous data and shows good agreement. This integrative approach is more comprehensive and is able to produce a more profound and detailed understanding between the sources and receptors, compared with single models.

[Analysis of Non-polar Organic Compounds in PM2.5 by Rapid Thermo-desorption Method Coupled with GC/MS].

Non-polar organic compounds (NPOCs) associated with PM2.5 in the atmosphere were analyzed by automated thermo-desorption (TD) coupled with gas chromatography/mass spectrometry (TD-GC/MS). The analyses for a total of 72 NPOCs were reviewed, including 34 PAHs, one Debenzothiophene, 27 alkanes (C10-C34), 5 hopanes and 5 steranes. Through this improved TD method, operation of filter loadings, TD condition and sample introduction were optimized. The MDL were 0.01-1.0, 0.1-8.0 and 0.50-2.0 ng·m-3 for PAHs, alkanes, hopanes and steranes, respectively. Calibration curve linearities were above 0.9 for all compounds. The TD efficiencies were 95%-100% for PAHs, 81%-100% for alkanes and 83.1%-100% for hopanes and steranes. PM2.5 samples were pretreated by TD and ultrasonic extraction methods separately and analyzed by GC/MS in two laboratories. Results from these two methods were comparable, as the relative biases were less than 30% for most compounds. Analysis results of PM2.5 samples from Linan and Shanghai showed that NPOCs were higher in winter than that in summer. Alkanes were predominant among NPOCs, followed by PAHs. Source analysis by PAH characteristic ratios indicated that fossil fuel burning and coal burning were the main sources of NPOCs in the two sites during the sampling periods.

Decadal changes in emissions of volatile organic compounds (VOCs) from on-road vehicles with intensified automobile pollution control: Case study in a busy urban tunnel in south China.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km-1 in 2014 against that of 194, 129, and 160 mg km-1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km-1; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km-1; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km-1, respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km-1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km-1. While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km-1 in 2004 to 449 ± 40 mg km-1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 103 mg km-1 in 2004 to 1.10 × 103 mg km-1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km-1 in 2004 to 25 mg km-1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards.

Impacts of particulate matter (PM2.5) on the behavior of freshwater snail Parafossarulus striatulus.

Fine particulate (PM2.5) is a severe problem of air pollution in the world. Although many studies were performed on examining effects of PM2.5 on human health, the understanding of PM2.5 influence on aquatic organisms is limited. Due to wet deposition, the pollutants in PM2.5 can enter aquatic ecosystems and affect aquatic organisms. This study tested the hypothesis that PM2.5 will negatively affect the behavior of freshwater snail Parafossarulus striatulus (Benson, 1842). Along with PM2.5, a number of components (Al, Pb, and Zn) that are commonly present in PM2.5 were also tested for their effects on the snail's behavior. The snail behavior was scored using the Behavioral State Score (BSS), ranging from 0 (no movement) to 5 (active locomotion and fully extended body). The result shows that high PM2.5 concentration dose (7.75 mg/L) induced a significant decrease in snails' movement behavior, and such reduced movement. The same behavior was also observed for treatments with chemical components related to PM2.5, including aluminum and acidity (pH 5.0). In contrast, a low concentration of PM2.5 (3.88 mg/L), lead, and zinc did not significantly affect snails' behavior. The results suggest that high PM2.5 deposition in water bodies, associated with acidification and some metals, can have an adverse effect on aquatic organisms.

Primary particulate emissions and secondary organic aerosol (SOA) formation from idling diesel vehicle exhaust in China.

In China diesel vehicles dominate the primary emission of particulate matters from on-road vehicles, and they might also contribute substantially to the formation of secondary organic aerosols (SOA). In this study tailpipe exhaust of three typical in-use diesel vehicles under warm idling conditions was introduced directly into an indoor smog chamber with a 30m3 Teflon reactor to characterize primary emissions and SOA formation during photo-oxidation. The emission factors of primary organic aerosol (POA) and black carbon (BC) for the three types of Chinese diesel vehicles ranged 0.18-0.91 and 0.15-0.51gkg-fuel-1, respectively; and the SOA production factors ranged 0.50-1.8gkg-fuel-1 and SOA/POA ratios ranged 0.7-3.7 with an average of 2.2. The fuel-based POA emission factors and SOA production factors from this study for idling diesel vehicle exhaust were 1-3 orders of magnitude higher than those reported in previous studies for idling gasoline vehicle exhaust. The emission factors for total particle numbers were 0.65-4.0×1015particleskg-fuel-1, and particles with diameters less than 50nm dominated in total particle numbers. Traditional C2-C12 precursor non-methane hydrocarbons (NMHCs) could only explain less than 3% of the SOA formed during aging and contribution from other precursors including intermediate volatile organic compounds (IVOC) needs further investigation.

Chemical characterization of humic-like substances (HULIS) in PM2.5 in Lanzhou, China.

Evaporative light scattering detection (ELSD) was applied to quantify HULIS (humic-like substances) for the first time in 2012 winter and 2013 summer at an urban site in Lanzhou. Water soluble organic carbon (WSOC), water soluble inorganic ions, and carbonaceous species (OC/EC) were also analyzed. The results show that OM (Organic Matter=OC×1.6, constituting 45.8% to PM2.5) was the most abundant species, followed by SNA (SO42-+NO3-+NH4+, constituting 23.4% to PM2.5). The chemical species were in the order of: OC>EC>SO42->NO3->NH4+>Cl->Ca2+>K+. The annual average concentration of HULIS was 4.70µg/m-3 and HULISc (carbon content of HULIS) contributed 6.19% to PM2.5 and 45.6% to WSOC, indicating that HULIS was the most important components of WSOC. The concentration of HULIS was 2.14±0.80µg/m3 in summer and 7.24±2.77µg/m3 in winter, respectively. The concentrations of HULIS were relatively low and stable in summer, while high and varied dramatically in winter. The abundance of HULISc in WSOC shows a more concentrated distribution in Lanzhou, with a range between 0.28-0.57. The ratios of HULIS/K+ were 6.25±1.41 and 6.14±1.96 in summer and winter, respectively, suggesting there were other significant sources in addition to biomass burning emissions. HULIS and WSOC exhibited similar seasonal variation and had a strong positive correlation. In addition to the good relationship (0.89) between HULIS and Cl- in winter, the great enhancement of HULIS with significantly high Cl- and relatively low K+ in winter indicated that residential coal burning was probably an important HULIS source in winter. Correlation and back trajectory analysis suggested that biomass burning and secondary formation were also important HULIS sources and the contribution of HULIS from dust could be neglected. Adverse meteorological conditions were also important factors for the accumulation of HULIS in winter.

Simultaneous monitoring and compositions analysis of PM1 and PM2.5 in Shanghai: Implications for characterization of haze pollution and source apportionment.

A year-long simultaneous observation of PM1 and PM2.5 were conducted at ECUST campus in Shanghai, the compositions were analyzed and compared. Results showed that PM2.5 was dominated by PM1 on clear days while the contribution of PM1-2.5 to PM2.5 increased on haze days, indicating that PM2.5 should be given priority to characterize or predict haze pollution. On haze days, accumulation of organic carbon (OC), elemental carbon (EC) and primary organic carbon (POC) in PM1-2.5 was faster than that in PM1. Humic-like substances carbon (Hulis-C) in both PM2.5 and PM1 formed faster than water soluble organic carbon (WSOC) on haze days, hence Hulis-C/WSOC increased with the intensification of haze pollution. In terms of water soluble ions, NO3(-)/SO4(2-) in PM1 increased with the aggravation of haze pollution, implying that mobile sources dominated on haze days, so is nitrogen oxidation ratio (NOR). Liquid water content (LWC) in both PM1 and PM2.5 had positive correlations with relative humidity (RH) but negative correlations with visibility, implying that hygroscopic growth might be a factor for visibility impairment, especially LWC in PM1. By comparison with multi-linear equations of LWC in PM1 and PM2.5, NO3(-) exerted a higher influence on hygroscopicity of PM1 than PM2.5, while RH, WSOC, SO4(2-) and NH4(+) had higher effects on PM2.5, especially WSOC. Source apportionment of PM2.5 was also investigated to provide reference for policy making. Cluster analysis by HYSPLIT (HYbrid Single Particle Lagrangian Integrated Trajectory) model showed that PM2.5 originated from marine aerosols, middle-scale transportation and large-scale transportation. Furthermore, PM2.5 on haze days was dominated by middle-scale transportation. In line with source apportionment by positive matrix factorization (PMF) model, PM2.5 was attributed to secondary inorganics, aged sea salt, combustion emissions, hygroscopic growth and secondary organics. Secondary formation was the principle source of PM2.5. Furthermore, the contribution of combustion emissions to PM2.5 increased with the intensification of haze pollution, which was just opposite to hygroscopic growth, while that of secondary formation kept quite stable on clear days and haze days.

Organosulfates from pinene and isoprene over the Pearl River Delta, South China: seasonal variation and implication in formation mechanisms.

Biogenic organosulfates (OSs) are important markers of secondary organic aerosol (SOA) formation involving cross reactions of biogenic precursors (terpenoids) with anthropogenic pollutants. Until now, there has been rare information about biogenic OSs in the air of highly polluted areas. In this study, fine particle (PM2.5) samples were separately collected in daytime and nighttime from summer to fall 2010 at a site in the central Pearl River Delta (PRD), South China. Pinene-derived nitrooxy-organosulfates (pNOSs) and isoprene-derived OSs (iOSs) were quantified using a liquid chromatograph (LC) coupled with a tandem mass spectrometer (MS/MS) operated in negative electrospray ionization (ESI) mode. The pNOSs with MW 295 exhibited higher levels in fall (151 ± 86.9 ng m(-3)) than summer (52.4 ± 34.0 ng m(-3)), probably owing to the elevated levels of NOx and sulfate in fall when air masses mainly passed through city clusters in the PRD and biomass burning was enhanced. In contrast to observations elsewhere where higher levels occurred at nighttime, pNOS levels in the PRD were higher during the daytime in both seasons, indicating that pNOS formation was likely driven by photochemistry over the PRD. This conclusion is supported by several lines of evidence: the specific pNOS which could be formed through both daytime photochemistry and nighttime NO3 chemistry exhibited no day-night variation in abundance relative to other pNOS isomers; the production of the hydroxynitrate that is the key precursor for this specific pNOS was found to be significant through photochemistry but negligible through NO3 chemistry based on the mechanisms in the Master Chemical Mechanism (MCM). For iOSs, 2-methyltetrol sulfate ester which could be formed from isoprene-derived epoxydiols (IEPOX) under low-NOx conditions showed low concentrations (below the detection limit to 2.09 ng m(-3)), largely due to the depression of IEPOX formation by the high NOx levels over the PRD.

Characterization of secondary aerosol and its extinction effects on visibility over the Pearl River Delta Region, China.

Aerosol samples collected from July 2007 to March 2008 were used to obtain major aerosol constituents in an urban location in the Pearl River Delta Region (PRD), China. The minimum organic carbon (OC)/elemental carbon (EC) ratio was used to calculate the primary and secondary organic carbon and the extinction effect of the secondary aerosol on visibility was estimated. As indicated in the analysis, the mass of secondary aerosol takes up 50% of the total mass of PM2.5; the OC/EC ratio is larger than 2 and there are significant characteristics of secondary aerosol generation; the levels of secondary OC are comparable with those of sulfate; and there is obvious enrichment of secondary aerosol on more polluted days. In a dry environment, the extinction weight is 59% for the secondary aerosol, while it is as high as 82% if the environment is highly humid (relative humidity [RH] = 95%). The hygroscopic growth of the aerosol can reduce visibility greatly; the secondary aerosol shares much larger quotas on more polluted days. For the Pearl River Delta (PRD), secondary aerosol and carbonaceous aerosol, especially secondary organic carbon (SOC), are a very acute problem; the study of the generating mechanism and sources for secondary aerosol is the key to the effort of controlling visibility in this region. The equation set forth in IMPROVE experiments can only be referenced but is not applicable to evaluate the extinction effect of individual aerosol components on visibility in the PRD region.

Mechanism-based quantitative structure-activity relationships for the inhibition of substituted phenols on germination rate of Cucumis sativus.

Comparative inhibition activity (GC50) of 42 structurally diverse substituted phenols on seed germination rate of Cucumis sativus was investigated. Quantitative structure-activity relationships (QSARs) were developed by using hydrophobicity (1-octanol/water partition coefficient, logKow) and electrophilicity (the energy of the lowest unoccupied molecule orbital, Eluma) for the toxicity of phenols according to their modes of toxic action. Most phenols elicited their response via a polar narcotic mechanism and a highly significant log Kow-based model was obtained (GC50 = 0.92 log Kow + 1.99, r2 0.84, n = 29). The inclusion of E(lumo) greatly improved the predictive power of the polar narcotic QSAR (GC50 = 0.88 log Kow - 0.30E(lumo) + 1.99, r2 = 0.93, n = 29). pKa proved to be an insignificant influencing factor in this study. Poor correlation with hydrophobicity and strong correlation with electrophilicity were observed for the nine bio-reactive chemicals. Their elevated toxicity was considerably underestimated by the polar narcotic logKow-dependent QSAR. The nine chemicals consist of selected nitro-substituted phenols, hydroquinone, catechol and 2-aminophenol. Their excess toxic potency could be explained by their molecular structure involving in vivo reaction with bio-macromolecules. Strong dissociation of carboxyl group of the four benzoic acid derivatives greatly decreased their observed toxicity. In an effort to model all chemicals including polar narcotics and bio-reactive chemicals, a response-surface analysis with the toxicity, logKow and E(lumo) was performed. This resulted in a highly predictive two-parameter QSAR for most of the chemicals (GC50 = 0. 70 logKow - 0.66E(lumo) + 2.17, r2 = 0.89, n = 36). Catechol and 2,4-dinitrophenol proved to be outliers of this model and their much high toxicity was explained.