A Newly Developed Aerosol Exposure Apparatus for Heated Tobacco Products for In Vivo Experiments Can Deliver Both Particles and Gas Phase With High Recovery and Depicts the Time-Dependent Variation in Nicotine Metabolites in Mouse Urine.

INTRODUCTION: There is no standardized aerosol exposure apparatus to deliver heated tobacco products (HTPs) for in vivo experiments. Therefore, we developed a novel HTPs aerosol exposure apparatus for mice and demonstrated that nicotine and other chemicals in HTPs aerosol generated by the apparatus can be delivered to mice which replicate human smoke. AIMS AND METHODS: The amounts of nicotine, tar, and carbon monoxide (CO) in IQOS (Marlboro Regular HeatSticks) aerosol generated by two types of apparatuses were determined. C57BL/6N mice were exposed to IQOS aerosol, followed by determination of the urinary nicotine metabolites. Further, the skin surface temperature of mice was monitored to confirm the vasoconstriction action of nicotine. RESULTS: The amount of chemicals in IQOS aerosol by the novel air push-in inhalation apparatus for HTPs (APIA) was equivalent to that of the analytical vaping machine (LM4E) (1.60 ± 0.08 [APIA] vs. 1.46 ± 0.07 mg/stick [LM4E] in nicotine and 0.55 ± 0.04 [APIA] vs. 0.45 ± 0.01 mg/stick [LM4E] in CO). After mice were exposed to IQOS aerosol by APIA, the urinary nicotine metabolite levels were determined; peak values in cotinine and 3-hydroxycotinine (3-HC) were 6.82 µg/mg creatinine at 1 hour after exposure and 32.9 µg/mg creatinine at 2 hours after exposure, respectively. The skin surface temperature decreased and was lower (33.5°C ± 0.5°C) at 30 minutes than before exposure (37.6°C ± 0.8°C). CONCLUSIONS: The new apparatus for HTPs aerosol exposure to mice showed good performances in terms of both chemical analysis of collected aerosol and fluctuations in the urinary nicotine metabolites. IMPLICATIONS: The APIA reported in this study can expose small animals to HTPs aerosol, including nicotine and other chemical substances as same amounts as LM4E and replicate actual human smoking process by in vivo experiments. Therefore, the experiments using APIA can provide evidence to assess the health risks of HTPs use.

Analysis of furans and pyridines from new generation heated tobacco product in Japan.

BACKGROUND: In recent years, heated tobacco products (HTPs), which are widely used in Japan, have been sold by various brands using additives such as flavors. It has been reported that the components of mainstream smoke are different from those of conventional cigarettes. In this study, we established an analytical method for furans and pyridines in the mainstream smoke, which are characteristic of HTPs and particularly harmful among the generated components, and investigated the amount of component to which the smokers are exposed. METHODS: We established a simple analytical method for simultaneous analysis of gaseous and particulate compounds in the mainstream smoke of HTPs (IQOS, glo, ploom S) in Japan by combining a sorbent cartridge and glass fiber filter (Cambridge filter pad (CFP)). Both the sorbent cartridge and CFP were extracted using 2-propanol and analyzed via GC-MS/MS to determine the concentration of furans and pyridines generated from each HTP. RESULTS: The results showed that the levels of target furans such as furfural, 2-furanmethanol, 2(5H)-furanone, and 5-methylfurfural tended to be higher in the mainstream smoke of glo than in standard cigarettes (3R4F). Pyridine, which is generated at a high level in 3R4F as a combustion component, and 4-ethenylpyridine (EP), which is a known marker of environmental tobacco smoke, were detected. Among these components, 2-furanmethanol and pyridine are classified as Group 2B (possibly carcinogenic to humans) by the International Agency for Research on Cancer (IARC). Therefore, it is possible that they will contribute to the health effects caused by use of HTPs. CONCLUSIONS: Using the new collection and analytical method for furans and pyridines in the mainstream smoke of HTPs, the level of each compound to which smokers are exposed could be clarified. By comprehensively combining information on the amount of ingredients and toxicity, it will be possible to perform a more detailed calculation of the health risks of using HTPs. In addition, the components detected in this study may be the causative substances of indoor pollution through exhaled smoke and sidestream smoke; therefore, environmental research on the chemicals generated from HTPs would be warranted in future studies.

Determination of Thermal Decomposition Products Generated from E-Cigarettes.

An electronic cigarette (e-cigarette) is a product used to smoke aerosol by heating a solution of "e-liquid" that consists of propylene glycol (PG) and glycerol (GLY) containing nicotine and flavors. In this study, thermal decomposition products generated from three brands of e-cigarettes were determined at various electric power levels. When using neat PG or GLY instead of e-liquid, propylene oxide was detected only in the gas phase from PG and not detected from GLY. In contrast, glycidol was detected only from GLY and not from PG. Almost all of the glyoxal and acrolein was detected from GLY, but formaldehyde and methyl glyoxal were detected from both PG and GLY. Using commercially available e-liquids, the same results were obtained. Nearly all chemical compounds generated from e-cigarettes have a carbon number of 3 or less except for nicotine and flavors. We measured chemical compounds generated from e-cigarettes at various electric power levels (1-85 W). At an electric power of 10 W, the generation of chemical compounds was very low; however, when the electric power exceeded 40 W, it increased exponentially. As thermal decomposition products of e-liquid, acetaldehyde, acrolein, and propylene oxide mainly occur as gaseous matter, while glyoxal, methylglyoxal, and glycidol mainly occur as particulate matter. Formaldehyde exits in both gaseous and particulate matter forms. Thermal decomposition products can be divided into three groups: thermal decomposition products originating from PG and GLY, those originating from other sources, and those directly generated. Concentrations of these thermal decomposition products were mostly higher than those in traditional cigarettes. In particular, thermal decomposition products generated from one of the studied e-cigarettes were very high; e.g., formaldehyde reached 4400 µg/15 puffs at 50 W. E-cigarette users must know that hazardous substances are generated even within the recommended electric power limits.

A novel analytical method for simple and low-cost detection of isocyanates in ambient air.

In this study, we developed a novel method for the collection of gaseous and particulate isocyanates in the air using di-n-butylamine (DBA)-coated glass fiber filters and a cation-exchange column (GFF_SCX-DBA) sampler. Our method showed acceptable linearity, accuracy, and precision in the analysis of eleven kinds of isocyanates (ICA, MIC, EIC, PIC, PHI, 1,6-HDI, 2,4-TDI, 2,6-TDI, trans-IPDI, cis-IPDI, and 4,4'-MDI). And, some of them were detected in the air at the plant manufacturing isocyanates and spray polyurethane foam. Actually, 2,4-TDI and 2,6-TDI (11,000 ± 6600 and 5800 ± 3500 ng/m3, respectively) were detected at much higher levels than others at the plant manufacturing isocyanates, and the levels of these isocyanates were comparable with those obtained by using the commercial sampler. Furthermore, PHI and 4,4'-MDI (5800 ± 470 and 3500 ± 1100 ng/m3, respectively) were detected at a relatively higher concentration than the others in the place of spray polyurethane foam. Through this study, we realized that the concentration of isocyanates in various working places could be analyzed using our GFF_SCX-DBA sampler. This method makes it possible to perform a rapid and simplified extraction operation in a shorter time than in the commercial sampler by combining the GFF and SCX samplers.

Simple Determination of Gaseous and Particulate Compounds Generated from Heated Tobacco Products.

As a new form of cigarettes, heated tobacco products (HTPs) have been rapidly distributed worldwide. In this study, an improved method for analyzing gaseous and particulate compounds generated from HTPs is described. Smoke is collected using a GF-CX572 sorbent cartridge with 300 mg of carbon molecular sieves, that is, Carboxen 572 (CX572), and a 9 mm glass-fiber filter (GF). After collection, the CX572 particles from the cartridge are transferred along with the GF and deposited into a vial containing two phases of carbon disulfide and methanol. The CX572 particles settle into the lower carbon disulfide phase, while nonpolar compounds are desorbed. After the sample is allowed to stand, the solution is slowly stirred. The two-phase mixture of carbon disulfide and methanol is combined into a homogeneous solution. Polar compounds are then desorbed, while the desorbed nonpolar compounds remain in solution. For the analysis of carbonyl compounds, an enriched 2,4-dinitrophenylhydrazine solution is added to a portion of the combined solution for derivatization and subsequent high-performance liquid chromatography analysis. For the analysis of volatile organic compounds and water, a portion of the combined solution is analyzed by gas chromatography-mass spectrometry or equipped with a thermal conductivity detector. By applying the proposed GF-CX572 one-cartridge method to the analysis of the mainstream smoke generated from HTPs and traditional cigarettes, several chemical compounds are detected, and the chemical composition of smoke is revealed. The GF-CX572 one-cartridge method can analyze gaseous and particulate chemical compounds from the HTP smoke by utilizing not only the entire puff volume but also one puff volume because the GF-CX-572 cartridge can be replaced with a new cartridge within 3 s. An overview of the chemicals generated from HTPs is obtained in detail by one-puff volume sampling. In addition, the generated chemical compounds strongly depend on the temperature of tobacco leaves in HTPs.

Analysis of isocyanates in indoor dust.

Isocyanates are harmful semi-volatile organic compounds that are emitted from various consumer products like polyurethane foam-based mattresses. Although it is a concern that isocyanates might accumulate in indoor dust, causing infants and toddlers, in particular, to be exposed to them, little information is available on the levels of isocyanates in the indoor environment. In this study, we investigated the suitability of an analytical method for determining the presence and level of isocyanates in the indoor dust. The method we developed displayed acceptable linearity, accuracy, and precision in the analysis of eleven different isocyanates. By using this analytical method, we could detect five isocyanates (ICA, MIC, EIC, PIC, and PHI) and quantify three isocyanates (MIC, EIC, and PHI) in indoor dust collected in different houses. This study is the first to focus on the pollution of indoor dust by isocyanates, and the tested method is suitable for the estimation of the level of isocyanate exposure. Graphical abstract ᅟ.

Spectrophotometric determination of ammonia levels in tobacco fillers of and sidestream smoke from different cigarette brands in Japan.

BACKGROUND: The ammonia contained in tobacco fillers and mainstream and sidestream cigarette smoke accelerates nicotine dependence in cigarette smokers. Ammonia has been included in the non-exhaustive priority list of 39 tobacco components and emissions of cigarette published by the World Health Organization (WHO) Study Group on Tobacco Product Regulation. The development of a simple ammonia detection method will contribute to the establishment of tobacco product regulation under tobacco control policies and allow surveys to be conducted, even by laboratories with small research budgets. METHODS: We developed a simple colorimetric method based on the salicylate-chlorine reaction and absorption spectrometry with two reagents (sodium nitroprusside and sodium dichloroisocyanurate). To compare this method to conventional ion chromatography, we analyzed the ammonia levels in tobacco fillers extracted from 35 Japanese commercially marketed cigarette brands manufactured by four tobacco companies (Japan Tobacco (JT) Inc., British American Tobacco (BAT), Philip Morris Japan, and Natural American Spirit). We also analyzed the ammonia levels in the sidestream smoke from cigarettes of the brands that were found to contain high or low tobacco filler ammonia levels. RESULTS: The ammonia levels in the reference cigarette (3R4F) measured by our method and ion chromatography were similar and comparable to previously reported levels. The ammonia levels in tobacco fillers extracted from 35 cigarette brands ranged from 0.25 to 1.58 mg/g. The mean ammonia level of JT cigarette brands was significantly higher (0.83 ± 0.28 mg/g) than that of Natural American Spirit cigarette brands (0.30 ± 0.08 mg/g) and lower than those in the other two cigarette brands (1.11 ± 0.19 mg/g for BAT and 1.24 ± 0.15 mg/g for Philip Morris) (p < 0.001 by Bonferroni test). The ammonia levels in the sidestream smoke of CABIN, Marlboro Black Menthol, American Spirit Light, and Seven Stars were 5.89 ± 0.28, 5.23 ± 0.12, 6.92 ± 0.56, and 4.14 ± 0.19 mg/cigarette, respectively. The ammonia levels were higher in sidestream smoke than in tobacco filler. CONCLUSIONS: Our simple colorimetric could be used to analyze ammonia in tobacco fillers and sidestream smoke. There were significant differences between the ammonia levels of the 35 commercially marketed cigarette brands in Japan manufactured by four tobacco manufacturers. Over 90% of the ammonia in sidestream smoke was in gaseous phase.

Comparison of Chemicals in Mainstream Smoke in Heat-not-burn Tobacco and Combustion Cigarettes.

Because of the health effects of secondhand smoke, the Japanese government is trying to establish an effective law for total avoidance of secondhand smoke in indoor environments for tobacco-free Tokyo Olympic and Paralympic games 2020, as requested by the International Olympic Committee (IOC) and the World Health Organization (WHO). Meanwhile, Philip Morris International has begun selling a new heat-not-burn tobacco, iQOS, which it claims is designed not to produce secondhand smoke. There is little scientific data, however, of the hazards and toxicity of iQOS. In this study, we evaluated several harmful compounds (nicotine, tar, carbon monoxide (CO) and tobacco-specific nitrosamines (TSNAs)) in the mainstream smoke and fillers of iQOS, and compared their concentrations with those from conventional combustion cigarettes. The concentrations of nicotine in tobacco fillers and the mainstream smoke of iQOS were almost the same as those of conventional combustion cigarettes, while the concentration of TSNAs was one fifth and CO was one hundredth of those of conventional combustion cigarettes. These toxic compounds are not completely removed from the mainstream smoke of iQOS, making it necessary to consider the health effects and regulation of iQOS.

Assessment of inhalation exposure to indoor air pollutants: Screening for health risks of multiple pollutants in Japanese dwellings.

Over the past few decades, multiple low level indoor pollutants have been found in domestic dwellings. The types and concentrations of these indoor pollutants have not been consistent over time and have changed with alterations in lifestyle, the development of novel products used in housing, and the development of new measurement technologies. To clarify the highest risk pollutants for which health risks should be reduced, we conducted a health risk assessment of 49 indoor air pollutants measured in 602 houses during winter and summer from 2012 to 2014. Inhalation reference concentrations were determined, and the margins of exposure were estimated for each indoor pollutant from measured indoor air concentrations. Health risks due to ammonia and acidic gases, including formic acid, acetic acid, and hydrogen chloride, were also assessed. Overall, during both winter and summer, the highest risk pollutants were acrolein, nitrogen dioxide, benzene, formic acid, and hydrogen chloride. The health risks of propanal, acetaldehyde, and 1,4-dichlorobenzene were also high. Principal component analysis (PCA) suggested an independent principal component for 1,4-dichlorobenzene. The primary source of exposure to 1,4-dichlorobenzene in Japan is an indoor household insect repellent. The improvement of individual lifestyle and housing may be appropriate targets for reducing the risk associated with this compound. The provision of further information on the risk to consumers and promotion of changes in consumer consciousness are needed. PCA suggested that the health risks of indoor air pollutants are amalgamated into similar chemical families, such as aldehydes, aliphatic hydrocarbons, aromatic hydrocarbons, or acetic esters. Our results suggest that health-based guidelines or source control measures, based on these chemical families and similar health endpoints, are appropriate for reducing total health risk due to multiple low level indoor pollutants.

Gaseous chemical compounds in indoor and outdoor air of 602 houses throughout Japan in winter and summer.

A nationwide survey of indoor air quality in Japan was conducted using four types of diffusive samplers. Gaseous chemical compounds such as carbonyls, volatile organic compounds (VOC), acid gases, basic gases, and ozone were measured in indoor and outdoor air of 602 houses throughout Japan in winter and summer. Four kinds of diffusive samplers were used in this study: DSD-BPE/DNPH packed with 2,4-dinitrophenyl hydrazine and trans-1,2-bis(2-pyridyl)ethylene coated silica for ozone and carbonyls; VOC-SD packed with Carboxen 564 particles for volatile organic compounds; DSD-TEA packed with triethanolamine impregnated silica for acid gases; and DSD-NH3 packed with phosphoric acid impregnated silica for basic gases. These samplers are small and lightweight and do not require a power source, hence, it was possible to obtain a large number of air samples via mail from throughout Japan. Almost all compounds in indoor air were present at higher levels in summer than in winter. In particular, formaldehyde, toluene, and ammonia were strongly dependent on temperature, and their levels increased with temperature. The nitrogen dioxide concentration in indoor air particularly increased only during winter and was well correlated with the formic acid concentration (correlation coefficient=0.959). Ozone concentrations in indoor air were extremely low compared with the outdoor concentrations. Ozone flowing from outdoor air may be decomposed quickly by chemical compounds in indoor air; therefore, it is suggested that the indoor/outdoor ratio of ozone represents the ventilation of the indoor environment.

Smoking topography and biomarkers of exposure among Japanese smokers: associations with cigarette emissions obtained using machine smoking protocols.

OBJECTIVES: Although the relative risk of lung cancer due to smoking is reported to be lower in Japan than in other countries, few studies have examined the characteristics of Japanese cigarettes or potential differences in smoking patterns among Japanese smokers. METHODS: To examine tar, nicotine and carbon monoxide (TNCO) emissions from ten leading cigarettes in Japan, machine smoking tests were conducted using the International Organization for Standardization (ISO) protocol and the Health Canada Intense (HCI) protocol. Smoking topography and tobacco-related biomarkers were collected from 101 Japanese smokers to examine measures of exposure. RESULTS: The findings indicate considerable variability in the smoking behavior of Japanese smokers. On average, puffing behaviors observed among smokers were more similar to the parameters of the HCI protocol, and brands with greater ventilation that yielded lower machine values using the ISO protocol were smoked more intensely than brands with lower levels of ventilation. The smokers of "ultra-low/low" nicotine-yield cigarettes smoked 2.7-fold more intensively than those of "medium/high" nicotine-yield cigarette smokers to achieve the same level of salivary cotinine (p = 0.024). CO levels in expiratory breath samples were associated with puff volume and self-reported smoking intensity, but not with nominal values of nicotine-yield reported on cigarette packages. CONCLUSIONS: Japanese smokers engaged in "compensatory smoking" to achieve their desired nicotine intake, and levels of exposure were greater than those suggested by the nominal value of nicotine and tar yields reported on cigarette packages.

Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis.

A typical method for the measurement of glutaraldehyde (GLA) employs 2,4-dinitrophenylhydrazine (DNPH) to form GLA-DNPhydrazone derivatives. However, this method is subject to analytical errors because GLA-DNPhydrazone is a quaternary bis-derivative and forms three geometric isomers (E-E, E-Z and Z-Z) as a result of the two C[double bond, length as m-dash]N double bonds. To overcome this issue, a method for transforming the C[double bond, length as m-dash]N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been applied. The amination reaction of GLA-DNPhydrazones with 2-picoline borane is accelerated with catalytic amounts of acid and is completed within 10 minutes in the presence of 100 mmol L(-1) phosphoric acid. Reduction of GLA-DNPhydrazone by 2-picoline borane is unique and results in the formation of N-(2,4-dinitrophenyl)-1-piperidinamine (DNPPA). NMR and LC-APCI-MS data confirmed the product identification. DNPPA is very stable and did not change when stored for at least four weeks at room temperature. DNPPA has excellent solubility of 14.6 g L(-1) at 20 °C in acetonitrile. The absorption maximum wavelength and the molar absorptivity of DNPPA were 351 nm and 4.2 × 10(4) L mol(-1) cm(-1) respectively. Complete separation between the reduced forms of C1-C10 aldehyde DNPhydrazones, including DNPPA, can be achieved by operating the reversed-phase high-performance liquid chromatograph at 351 nm in gradient mode using a C18 amide column. The reductive amination method for GLA overcomes analytical errors caused by E-E, E-Z and Z-Z geometrical isomers.

[Determination of tobacco-specific N'-nitrosamines in mainstream smoke from Japanese cigarettes].

OBJECTIVES: Mainstream smoke from cigarettes contains tobacco-specific N'-nitrosamines (TSNAs) listed as Group 1 and 3 carcinogens by the International Agency for Research on Cancer (IARC). Herein, we report on a method of measuring the concentrations of TSNAs in mainstream smoke from the ten top-selling Japanese cigarette brands using an ISO regime by International Organization for Standardization (ISO) and HCI regime of Health Canada. METHODS: Tar in mainstream smoke was collected on a Cambridge filter pad using a smoking machine. The filter pad was immersed in 40 mL of ammonium acetate (pH 6.8) and shaken for 30 min. The extract was then loaded into a C18 column. After washing with 5 mL of 10% methanol and eluting with 5 mL of 70% methanol, the eluate was concentrated to 1 mL for LC-MS/MS analysis. RESULTS: The concentrations of TSNAs in all cigarette brands were higher when determined using the HCI regime than when determined using the ISO regime. Furthermore, the concentrations of TSNAs measured using both the ISO and HCI regimes showed negligible correlation to the tar and nicotine concentrations indicated on package labels. The cigarette samples used in the study were categorized into four classes: ultralow-, low-, medium-, and high-yield brands, which corresponded to 1, 3-6, 8-10, and 14 mg tar/cigarette, respectively. The concentration of TSNAs in ultralow-yield cigarettes was 210 ng/cigarette, as measured using the HCI regime, which was nearly equal to that in high-yield cigarettes (180 ng/cigarette). CONCLUSIONS: Exposure to TSNAs from mainstream smoke from ultralow-yield cigarettes is comparable to that from high-yield cigarettes. To properly evaluate the risk of smoking, not only the concentrations of tar and nicotine but also those of other chemicals, including TSNAs, should be printed on package labels.

Health Risk Assessment Based on Exposure to Chemicals in Air.

Few studies have investigated personal exposure concentrations of not only some volatile organic compounds but also more types of chemicals including acidic gases and acrolein. We measured the personal exposure concentrations of 35 chemicals including these chemicals in indoor and outdoor air in Chiba-shi, Japan, for 7 days in summer and winter to assess the associated health risks in 22 people. The personal exposure concentrations of nitrogen dioxide were higher in winter than in summer, and those of formaldehyde, p-dichlorobenzene, and tetradecane were higher in summer than in winter. The personal exposure concentrations were mostly equal to or lower than the concentrations in indoor air, contrary to the results of a lot of previous studies. The high-risk chemicals based on personal exposure concentrations were identified as acrolein (max. 0.43 µg/m3), benzene (max. 3.1 µg/m3), and hexane (max. 220 µg/m3) in summer, and acrolein (max. 0.31 µg/m3), nitrogen dioxide (max. 320 µg/m3), benzene (max. 5.2 µg/m3), formic acid (max. 70 µg/m3), and hexane (max. 290 µg/m3) in winter. In addition, we estimated personal exposure concentrations according to the time spent at home and the chemical concentrations in indoor and outdoor air. We found that the estimated concentrations of some participants largely differed from the measured ones indicating that it is difficult to estimate personal exposure concentrations based on only these data.

Simple Ozone Scrubber Using a Glass Fiber Filter Impregnated with Hydroquinone for the Quantitative Analysis of Ambient Air Samples.

As a standard method for measuring the concentration of carbonyl compounds in air, 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high-performance liquid chromatography (HPLC) is widely used. However, the method is often plagued by interference issues related to the ozone content in ambient air samples. Although the use of a potassium iodide (KI) scrubber circumvents these problems, the combination of a DNPH-coated silica cartridge and KI scrubber often performs poorly, particularly in high humidity. The KI in the scrubber becomes wet under these conditions, trapping the carbonyl compounds under investigation before they can reach the DNPH cartridge; this ultimately results in inaccurate readings. In this study, a new type of ozone scrubber consisting of a glass fiber filter coated with hydroquinone (HQF) was developed. The HQF scrubber was placed in front of the DNPH-coated silica cartridge, allowing airborne carbonyl compounds to pass unimpeded through the HQF section before being trapped by the DNPH-coated silica. The subsequent reaction of the trapped carbonyls with DNPH produced carbonyl 2,4-DNPhydrazone derivative that is used as the basis for the quantitative and qualitative analyses of ambient air samples. The hydroquinone in HQF reacts with ozone to form benzoquinone with an efficiency of more than 95% under wide relative humidity range (8 - 95%). The performance of our novel HQF scrubber was compared with those of potassium iodide (KI) and our previously developed trans-1,2-bis(2-pyridyl)ethylene (BPE)-coated silica scrubbers using ambient air samples, and the results showed that both HQF-DNPH and BPE-DNPH cartridges detected carbonyl compounds in the same concentration levels. The proposed method is superior to the KI-based and BPE-based technique for ozone removal because the HQF is very small and can be easily attached to any commercially available DNPH cartridge.

Spatial Variations of Indoor Air Chemicals in an Apartment Unit and Personal Exposure of Residents.

Indoor air quality (IAQ) can greatly affect health in people spending much time indoors. However, the influence of IAQ on personal exposure to chemical compounds in Japan remains poorly investigated. Hence, this study aimed to clarify this influence thoroughly within one apartment. We surveyed the concentrations of 61 chemical compounds in the air in nine different spaces within an apartment unit, as well as the personal exposure of two residents in Japan. Using three kinds of diffusive samplers, this study was conducted continuously for 7 days in summer and winter. Health risks were evaluated by calculating the margin of exposure (MOE) using the measured concentrations. Some chemical concentrations showed large spatial variations and the personal exposure concentrations of these compounds also differed among residents. According to the calculated MOE, the chemicals with the highest health risk were acrolein, p-dichlorobenzene, and acetaldehyde in summer and acrolein, nitrogen dioxide, formic acid, p-dichlorobenzene, and benzene in winter. The IAQ of the house could be divided in two, and the IAQ in the space where residents spent much time (i.e., bedroom) highly affected each of the residents' exposure. Investigating chemical concentrations in multiple spaces (including bedroom and living room) is necessary to understand the effect of IAQ on personal exposure.

Indoor Formaldehyde Concentration, Personal Formaldehyde Exposure and Clinical Symptoms during Anatomy Dissection Sessions, University of Medicine 1, Yangon.

The formaldehyde (FA) embalming method, the world's most common protocol for the fixation of cadavers, has been consistently used in medical universities in Myanmar. This study was designed to examine the indoor FA concentrations in anatomy dissection rooms, an exposed site, and lecture theater, an unexposed control site, and to access personal exposure levels of FA and clinical symptoms of medical students and instructors. In total, 208 second year medical students (1/2019 batch) and 18 instructors from Department of Anatomy, University of Medicine 1, participated. Thirteen dissection sessions were investigated from February 2019 to January 2020. Diffusive sampling devices were used as air samplers and high-performance liquid chromatography was used for measurement of FA. Average indoor FA concentration of four dissection rooms was 0.43 (0.09-1.22) ppm and all dissection rooms showed indoor concentrations above the occupational exposure limits and short-term exposure limit for general population. Personal FA exposure values were higher than indoor FA concentrations and the instructors (0.68, 0.04-2.11 ppm) had higher exposure than the students (0.44, 0.06-1.72 ppm). Unpleasant odor, eye and nose irritations and inability to concentrate were frequently reported FA-related symptoms, and the students were found to have significantly higher risks (p < 0.05) of having these symptoms during the dissection sessions than during lecture.

Reductive amination of aldehyde 2,4-dinitorophenylhydrazones using 2-picoline borane and high-performance liquid chromatographic analysis.

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DNPhydrazones form both E- and Z-geometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carried out by adding 2-picoline borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of C(1)-C(10) aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from C(1)-C(10) aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 x 10(4) (C(1)) to 2.2 x 10(4) L/mol/cm (C(10)). Complete separation between C(1)-C(10) aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascentis RP-Amide column (150 mm x 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers.

Improved measurement of ozone and carbonyls using a dual-bed sampling cartridge containing trans-1,2-bis(2-pyridyl)ethylene and 2,4-dinitrophenylhydrazine-impregnated silica.

We have previously developed a new method using trans-1,2-bis-(4-pyridyl)ethylene (4-BPE) and 2,4-dinitrophenylhydrazine (DNPH) for the simultaneous determination of ozone and carbonyls in air using a two-bed cartridge system. In this method, 4-BPE was used to capture ozone. However, the method suffered from long reaction times in the eluate, low solubility of the DNPH derivative, and a strong dependence on atmospheric moisture. These problems could be overcome by using trans-1,2-bis-(2-pyridyl)ethylene (2-BPE) in place of 4-BPE. The efficiency of the reaction of ozone with 2-BPE to form pyridine-2-aldehyde (2PA) is higher than the corresponding reaction with 4-BPE. Under the optimized elution conditions, the reaction times of 2PA and 4PA with DNPH are within 15 and 120 min, respectively. In the elution from the sampling cartridge, 2PA formed from 2-BPE and ozone is easier to dissolve in the elution solvent. A stronger influence of humidity was observed in ozone recovery by the 4-BPE/DNPH method. 2-BPE exhibits a maximum reaction efficiency of 84% at 32% relative humidity (RH), while 4-BPE attains a maximum reaction efficiency of 82% at 49% RH. Humidity has much less influence on the reaction of 2-BPE with ozone. Above 18% RH, the reaction efficiency of 2-BPE with ozone is in the range 80-84%. Thus, 2-BPE is the more useful reagent for ozone analysis. The concentrations of ozone and carbonyls by the improved 2-BPE/DNPH method corresponded with the mean value by an ozone auto analyzer in an air monitoring station and a DNPH cartridge coupled with a KI-ozone scrubbing cartridge.

Simultaneous determination of ozone and carbonyls using trans-1,2-bis(4-pyridyl)ethylene as an ozone scrubber for 2,4-dinitrophenylhydrazine-impregnated silica cartridge.

A new method for the simultaneous determination of ozone and carbonyls in air using a two-bed cartridge system has been developed. Each bed consists of reagent-impregnated silica particles. The first contains trans-1,2-bis-(4-pyridyl) ethylene (BPE) while the second contains 2,4-dinitrophenylhydrazine (DNPH). Air samples are drawn through the cartridge first through the BPE and then through the DNPH. Ozone in the air sample is trapped in the first bed by the BPE-coated silica particles and produce pyridine-4-aldehyde. Airborne carbonyls pass unimpeded thorough the BPE and are trapped in the second bed by the DNPH-coated silica particles. They produce carbonyl 2,4-DNPhydrazones. DNPH and carbonyl 2,4-DNPhydrazones are not influenced by ozone because of effective trapping by the BPE. Extraction is performed in the direction reverse to air sampling. When solvent is eluted through the BEP/DNPH cartridge, excess DNPH is washed into the BPE bed where it reacted with pyridine-4-aldehyde and forms the corresponding hydrazone derivative. All of the hydrazones derived from airborne carbonyls and pyridine-4-aldehyde (derived from ozone) are completely separated and measured using high-performance liquid chromatography. An Ascentis RP-Amide column is used, and the mobile phase is 40% aqueous acetonitrile containing 2 mmol/L ammonium acetate. The use of a BPE/DNPH cartridge has made possible the simultaneous determination of ozone and carbonyls. A separate ozone scrubber is not necessary with the BPE/DNPH cartridge because the BPE portion of the sampler serves this function.