Characterizing Chemical, Environmental, and Stimulated Subcellular Physical Characteristics of Size-Fractionated PMs Down to PM0.1.

Air pollution, especially particulate matter (PM), is a significant environmental pollution worldwide. Studying the chemical, environmental, and life-related cellular physical characteristics of size-fractionated PMs is important because of their different degrees of harmful effects on human respiratory tracts and organ systems, causing severe diseases. This study evaluates the chemical components of size-fractionated PMs down to PM0.1 collected during a biomass-burning episode, including elemental/organic carbon and trace elements. Single particle sizes and distributions of PM0.1, PM0.5-0.1, PM1.0-0.5, and PM2.5-1.0 were analyzed by scanning electron microscopy and Zeta sizer. Two commonly used cell lines, e.g., HeLa and Cos7 cells, and two respiratory-related cell lines including lung cancer/normal cells were utilized for cell cytotoxicity experiments, revealing the key effects of particle sizes and concentrations. A high-speed scanning ion conductance microscope explored particle-stimulated subcellular physical characteristics for all cell lines in dynamics, including surface roughness (SR) and elastic modulus (E). The statistical results of SR showed distinct features among different particle sizes and cell types while a E reduction was universally found. This work provides a comprehensive understanding of the chemical, environmental, and cellular physical characteristics of size-fractionated PMs and sheds light on the necessity of controlling small-sized PM exposures.

Simulation analysis of hazardous chemicals released from the furniture plant using ALOHA software.

The manufacturing of wooden furniture is extensive in Thailand's east. Hazardous chemicals were used in the wooden furniture industry's manufacturing process. Hazardous substances released into the surrounding atmosphere appear to have an impact on the environment and individuals. The ALOHA model is frequently used to assess hazardous chemicals released into the environment; this simulation model is an effective tool for modeling chemical compounds and detecting chemical disasters. It has a tremendous potential for preventing mishaps in potentially hazardous or emergency situations. Acetone and butyl acetate were extracted from the hardwood furniture business to identify accidents such as leaking, spillage, and evaporation. It is described as a highly poisonous, combustible, and explosive material. Toxic accident releases have negative implications for the surrounding areas. The goal of this work was to examine each accident using ALOHA software, and the computation of acetone and butyl acetate accidents was shown in this study. This project provides critical data for the furniture plant's chemical emergency rescue strategy as well as recommendations for emergency evacuation site decision-making.

The influence of the open burning of agricultural biomass and forest fires in Thailand on the carbonaceous components in size-fractionated particles.

Size-segregated ambient particles down to particles smaller than 0.1 µm (PM0.1) were collected during the year 2014-2015 using cascade air samplers with a PM0.1 stage, at two cities in Thailand, Bangkok and Chiang Mai. Their characteristics and seasonal behavior were evaluated based on the thermal/optical reflectance (IMPROVE_TOR) method. Diagnostic indices for their emission sources and the black carbon (BC) concentration were assessed using an aethalometer and related to the monthly emission inventory (EI) of particle-bound BC and organic carbon (OC) in order to investigate the contribution of agricultural activities and forest fires as well as agro-industries in Thailand. Monthly provincial EIs were evaluated based on the number of agricultural crops produced corresponding to field residue burning and the use of residues as fuel in agro-industries, and also on the number of hot spots from satellite images corresponding to the areas burned by forest fires. The ratio of char-EC/soot-EC describing the relative influence of biomass combustion to diesel emission was found to be in agreement with the EI of BC from biomass burning in the size range <1 µm. This was especially true for PM0.1, which usually tends to be indicative of diesel exhaust particles, and was shown to be very sensitive to the EI of biomass burning. In Chiang Mai, the northern part of Thailand, the forest fires located upwind of the monitoring site were found to be the largest contributor while the carbon behavior at the site in Bangkok was better accounted for by the EI of provinces in central Thailand including Bangkok and its surrounding provinces, where the burning of crop residues and the cultivation of sugarcane for sugar production are significant factors. This suggests that the influence of transportation of polluted air masses is important on a multi-provincial scale (100-200 km) in Thailand.

Personal inhalation exposure to polycyclic aromatic hydrocarbons and their nitro-derivatives in rural residents in northern Thailand.

A personal inhalation exposure and cancer risk assessment of rural residents in Lampang, Thailand, was conducted for the first time. This highlighted important factors that may be associated with the highest areal incidence of lung cancer. Personal exposure of rural residents to polycyclic aromatic hydrocarbons (PAHs) and their nitro-derivatives (NPAHs) through inhalation of fine particulate matter (PM2.5) was investigated in addition to stationary air sampling in an urban area. The personal exposure of the subjects to PM2.5 ranged from 44.4 to 316 µg/m3, and the concentrations of PAHs (4.2-224 ng/m3) and NPAHs (120-1449 pg/m3) were higher than those at the urban site, indicating that personal exposure was affected by microenvironments through individual activities. The smoking behaviors of the rural residents barely affected their exposure to PAHs and NPAHs compared to other sources. The most important factor concerning the exposure of rural populations to PAHs was cooking activity, especially the use of charcoal open fires. The emission sources for rural residents and urban air were evaluated using diagnostic ratios, 1-nitropyrene/pyrene, and benzo[a]pyrene/benzo[ghi]perylene. Their analyses showed a significant contribution to emission from residents' personal activities in addition to the atmospheric environment. Furthermore, the personal inhalation cancer risks for all rural subjects exceeded the USEPA guideline value, suggesting that the residents have a potentially increased cancer risk. The use of open fires showed the highest cancer risk. A reduction in exposure to air pollutants for the residents could potentially be achieved by using clean fuel such as liquid petroleum gas or electricity for daily cooking.

Simultaneous determination of urinary hydroxylated metabolites of naphthalene, fluorene, phenanthrene, fluoranthene and pyrene as multiple biomarkers of exposure to polycyclic aromatic hydrocarbons.

A method is presented for determining monohydroxy polycyclic aromatic hydrocarbons (OHPAHs) having 2-, 3- and 4-rings in human urine by using high-performance liquid chromatography with fluorescence detection. A urine sample containing conjugates of OHPAHs was hydrolysed in the presence of beta-glucuronidase/aryl sulfatase and the solution was cleaned up with a solid-phase extraction (C(18) and silica). Eight OHPAHs, namely 1- and 2-hydroxynaphthalenes, 2-hydroxyfluorene, 2-, 3- and 4-hydroxyphenanthrenes, 3-hydroxyfluoranthene and 1-hydroxypyrene, were separated and 1- and 9-hydroxyphenanthrenes co-eluted on an alkylamide-type reversed-phase column with fluorimetric detection. The urinary concentrations of OHPAHs were quantified by using deuterated 1-hydoxypyrene as an internal standard. The method showed good repeatability for inter- and intra-day precisions as well as good linearity of calibration curves (r (2) ranged from 0.996 to 0.999). The limits of detection (S/N=3) were in the range from 2.3 fmol to 2.2 pmol per injection. This method was successfully applied to urine samples from non-smoking taxi drivers, traffic policemen and rural villagers of Chiang Mai, Thailand. The results showed higher urinary concentrations of OHPAHs in rural villagers, consistent with higher respiratory exposure to PAHs.

Hair analysis of nicotine and cotinine for evaluating tobacco smoke exposure by liquid chromatography-mass spectrometry.

A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision.

Quantification of 2-hydroxyfluorene in human urine by column-switching high performance liquid chromatography with fluorescence detection.

A high performance liquid chromatographic (HPLC) method for the quantification of 2-hydroxyfluorene (2-OHF) in normal human urine was established using deuterated 2-hydroxyfluorene (2-OHF-d9) as an internal standard with column-switching and fluorescence detection. The 2-OHF-d9 was synthesized by the metabolism of deuterated fluorene with cytochrome P450. The analytes were cleaned up on an ODS pre-column, via column-switching, and separated on an alkylamide-type reversed phase column. The internal standard eluted immediately prior to non-deuterated 2-OHF on the HPLC system and had nearly the same fluorescence characteristics as the non-deuterated 2-OHF. The detection limit was 0.03 nmol l(-1) (S/N = 3) and the calibration range of urine sample was from 0.2 to 50 nmol l(-1). The urine sample treatment involved enzymatic hydrolysis followed by solid phase extraction using a Sep-Pak C18 cartridge. 2-OHF was observed in the form of conjugates such as glucuronide and/or sulfate in human urine, and urinary metabolites were completely hydrolyzed for 2 h with beta-glucuronidase/aryl sulfatase. The proposed method was used to determine urinary 2-OHF in smokers and non-smokers, and showed that the urinary concentrations of 2-OHF in smokers were significantly higher than those in non-smokers (P < 0.01). Thus, the data suggest that urinary 2-OHF might be a sensitive and specific biological marker for the assessment of the exposure to polycyclic aromatic hydrocarbons.

Quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair by HPLC with fluorescence detection: a biological monitoring method to evaluate the exposure to PAHs.

A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

Method for determining monohydroxybenzo[a]pyrene isomers using column-switching high-performance liquid chromatography.

A method for determining monohydroxybenzo[a]pyrene (OHBaP) isomers using column-switching high-performance liquid chromatography with fluorescence detection was developed. Eleven of 12 isomers of OHBaP (all except 6-OHBaP) were separated on an alkylamide-type reversed-phase column and, via column-switching, on a beta-cyclodextrin-bonded silica gel column. The detection limits for the OHBaPs were in the range 0.3-8 pg/injection (S/N=3). By using this method, 1-, 3-, and 9-OHBaPs were identified as major metabolites of benzo[a]pyrene in vitro by human recombinant p450 1A1. The method was used to determine OHBaPs in the urine of a nonsmoker subject. After enzymatic hydrolysis of the conjugated metabolites by beta-glucuronidase/aryl sulfatase, the analytes were selectively adsorbed on blue rayon (a cellulose-supported copper phthalocyanine) from the urine matrix. Methanol as the eluting solvent from the rayon gave the best recoveries of OHBaPs and 1-hydroxypyrene (1-OHP) in the range of 91-103%, which was superior to that of the solid-phase extraction method. 1-OHP, a well-known biomarker of the exposure to polycyclic aromatic hydrocarbons, was simultaneously analyzed. Intra- and interday accuracy values for the determination of 3-OHBaP in 200 ml of urine were 95.5 and 100.9%, and those for 1-OHP were 96.4 and 103.6%, respectively. The intra- and interday precision values were 3.9 and 2.4% for 3-OHBaP and 2.4 and 3.2% for 1-OHP, respectively. In 11 kinds of isomers, only 3-OHBaP was detected in the human urine. Urinary concentration of 3-OHBaP was quantified at 0.5 ng/g creatinine concentration and the 3-OHBaP/1-OHP ratio was approximately 1/130.

Determination of 1-hydroxypyrene in human urine by high-performance liquid chromatography with fluorescence detection using a deuterated internal standard.

A high-performance liquid chromatographic method has been developed for the quantification of 1-hydroxypyrene (1-OHP) in human urine using deuterated 1-hydroxypyrene ([2H9]1-OHP) as an internal standard with fluorescence detection. [2H9]1-OHP was prepared enzymatically from deuterated pyrene ([2H10]Pyr) with cytochrome P450 1A1. It eluted immediately prior to non-deuterated 1-OHP on alkylamide-type reversed-phase columns and had nearly the same fluorescence characteristics as non-deuterated 1-OHP. The detection limit was 0.1 microg/L and the calibration range was from 1 to 100 nmol/L. Urine sample treatment involved enzymatic hydrolysis followed by solid-phase extraction using Sep-Pak C18 cartridges. The proposed method was used to determine urinary 1-OHP in smokers and non-smokers.