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BACKGROUND: Particulate matter (PM) is recognized as the most harmful air pollutant to the human health. The Yangon city indeed suffers much from PM-related air pollution. Recent research has interestingly been focused on the novel subject of changes in the air quality associated with the restrictive measures in place during the current coronavirus disease-2019 (COVID-19) pandemic. The first case of COVID-19 in Myanmar was diagnosed on March 23, 2020. In this article, we report on our attempt to evaluate any effects of the COVID-19-restrictive measures on the ambient PM pollution in Yangon. METHODS: We measured the PM concentrations every second for 1 week on four occasions at three study sites with different characteristics; the first occasion was before the start of the COVID-19 pandemic and the remaining three occasions were while the COVID-19-restrictive measures were in place, including Stay-At-Home and Work-From-Home orders. The Pocket PM2.5 Sensor [PRO] designed by the National Institute for Environmental Studies (NIES), Japan, in cooperation with Yaguchi Electric Co., Ltd., (Miyagi, Japan) was used for the measurement of the ambient PM2.5 and PM10 concentrations. RESULTS: The results showed that there was a significant reduction (P < 0.001) in both the PM2.5 and PM10 concentrations while the COVID-19-restrictive measures were in place as compared to the measured values prior to the pandemic. The city experienced a profound improvement in the PM-related air quality from the "unhealthy" category prior to the onset of the COVID-19 pandemic to the "good" category during the pandemic, when the restrictive measures were in place. The percent changes in the PM concentrations varied among the three study sites, with the highest percent reduction noted in a semi-commercial crowded area (84.8% for PM2.5; 88.6% for PM10) and the lowest percent reduction noted in a residential quiet area (15.6% for PM2.5; 12.0% for PM10); the percent reductions also varied among the different occasions during the COVID-19 pandemic that the measurements were made. CONCLUSIONS: We concluded that the restrictive measures which were in effect to combat the COVID-19 pandemic had a positive impact on the ambient PM concentrations. The changes in the PM concentrations are considered to be largely attributable to reduction in anthropogenic emissions as a result of the restrictive measures, although seasonal influences could also have contributed in part. Thus, frequent, once- or twice-weekly Stay-At-Home or Telework campaigns, may be feasible measures to reduce PM-related air pollution. When devising such an action plan, it would be essential to raise the awareness of public about the health risks associated with air pollution and create a social environment in which Telework can be carried out, in order to ensure active compliance by the citizens.
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Poluição do Ar/análise , COVID-19/epidemiologia , Material Particulado/análise , Humanos , Mianmar/epidemiologia , Pandemias , SARS-CoV-2RESUMO
Fine particulate matter (PM2.5) in the atmosphere is of high priority for air quality management efforts to address adverse health effects in human. We believe that emission control policies, which are traditionally guided by source contributions to PM mass, should also consider source contributions to PM health effects or toxicity. In this study, we estimated source contributions to the toxic potentials of organic aerosols (OA) as measured by a series of chemical and in-vitro biological assays and chemical mass balance model. We selected secondary organic aerosols (SOA), vehicles, biomass open burning, and cooking as possible important OA sources. Fine particulate matter samples from these sources and parallel atmospheric samples from diverse locations and seasons in East Asia were collected for the study. The source and atmospheric samples were analyzed for chemical compositions and toxic potentials, i.e. oxidative potential, inflammatory potential, aryl hydrocarbon receptor (AhR) agonist activity, and DNA-damage, were measured. The toxic potentials per organic carbon (OC) differed greatly among source and ambient particulate samples. The source contributions to oxidative and inflammatory potentials were dominated by naphthalene-derived SOA (NapSOA), followed by open burning and vehicle exhaust. The AhR activity was dominated by open burning, followed by vehicle exhaust and NapSOA. The DNA damage was dominated by vehicle exhaust, followed by open burning. Cooking and biogenic SOA had smaller contributions to all the toxic potentials. Regarding atmospheric OA, urban and roadside samples showed stronger toxic potentials per OC. The toxic potentials of remote samples in summer were consistently very weak, suggesting that atmospheric aging over a long time decreased the toxicity. The toxic potentials of the samples from the forest and the experimentally generated biogenic SOA were low, suggesting that toxicity of biogenic primary and secondary particles is relatively low.
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Poluentes Atmosféricos , Poluição do Ar , Aerossóis/análise , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/toxicidade , Poluição do Ar/análise , Monitoramento Ambiental , Ásia Oriental , Humanos , Material Particulado/análise , Material Particulado/toxicidade , Estações do AnoRESUMO
Thousands of organohalogen compounds, including hazardous chemicals such as polychlorinated biphenyls (PCBs) and other persistent organic pollutants (POPs), were selectively and simultaneously detected and identified with simple, or no, purification from environmental sample extracts by using several advanced methods. The methods used were software extraction from two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (GC × GC-HRTofMS) data, measurement by negative chemical ionization with HRTofMS, and neutral loss scanning (NLS) with GC × GC-MS/MS. Global and selective detection of organochlorines and bromines in environmental samples such as sediments and fly ash was achieved by NLS using GC × GC-MS/MS (QQQ), with the expected losses of 35Cl and 79Br. We confirmed that negative chemical ionization was effective for sensitive and selective ionization of organohalogens, even using GC × GC-HRTofMS. The 2D total ion chromatograms obtained by using negative chemical ionization and selective extraction of organohalogens using original software from data measured by electron impact ionization were very similar; the software thus functioned well to extract organohalogens. Combining measurements made by using these different methods will help to detect organohalogens selectively and globally. However, to compare the data obtained by individual measurements, the retention times of the peaks on the 2D chromatograms need to match.
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Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Cromatografia Gasosa-Espectrometria de Massas , Hidrocarbonetos Halogenados/análise , Espectrometria de Massas em Tandem , Mineração de Dados , Poluentes Ambientais/química , Hidrocarbonetos Halogenados/química , Software , Fatores de TempoRESUMO
Poor air quality is globally the largest environmental health risk. Epidemiological studies have uncovered clear relationships of gaseous pollutants and particulate matter (PM) with adverse health outcomes, including mortality by cardiovascular and respiratory diseases. Studies of health impacts by aerosols are highly multidisciplinary with a broad range of scales in space and time. We assess recent advances and future challenges regarding aerosol effects on health from molecular to global scales through epidemiological studies, field measurements, health-related properties of PM, and multiphase interactions of oxidants and PM upon respiratory deposition. Global modeling combined with epidemiological exposure-response functions indicates that ambient air pollution causes more than four million premature deaths per year. Epidemiological studies usually refer to PM mass concentrations, but some health effects may relate to specific constituents such as bioaerosols, polycyclic aromatic compounds, and transition metals. Various analytical techniques and cellular and molecular assays are applied to assess the redox activity of PM and the formation of reactive oxygen species. Multiphase chemical interactions of lung antioxidants with atmospheric pollutants are crucial to the mechanistic and molecular understanding of oxidative stress upon respiratory deposition. The role of distinct PM components in health impacts and mortality needs to be clarified by integrated research on various spatiotemporal scales for better evaluation and mitigation of aerosol effects on public health in the Anthropocene.
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Aerossóis , Poluentes Atmosféricos , Estudos Epidemiológicos , Poluição do Ar , Material ParticuladoRESUMO
Progress on the fabrication of ultrahigh-Q photonic-crystal nanocavities (PhC-NCs) has revealed the prospect for new applications including silicon Raman lasers that require a strong confinement of light. Among various PhC-NCs, the highest Q has been recorded with silicon. On the other hand, microcavity is one of the basic building blocks in silicon photonics. However, the fusion between PhC-NCs and silicon photonics has yet to be exploited, since PhC-NCs are usually fabricated with electron-beam lithography and require an air-bridge structure. Here we show that a 2D-PhC-NC fabricated with deep-UV photolithography on a silica-clad silicon-on-insulator (SOI) structure will exhibit a high-Q of 2.2 × 10(5) with a mode-volume of ~ 1.7(λ/n)(3). This is the highest Q demonstrated with photolithography. We also show that this device exhibits an efficient thermal diffusion and enables high-speed switching. The demonstration of the photolithographic fabrication of high-Q silica-clad PhC-NCs will open possibility for mass-manufacturing and boost the fusion between silicon photonics and CMOS devices.
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We developed a method that can accurately calculate the theoretical quality factor (Q) of a two-dimensional photonic crystal slab nanocavity at a very high speed. Because our method is based on a direct calculation of the out-of-slab radiation loss rate, it does not suffer from in-plane loss, and this allows us to obtain the same Q with 0.18 times less calculation volume. In addition, we can obtain the Q immediately after finishing the cavity excitation, because our method uses only a snapshot of the wavevector space distribution of the resonant mode in contrast to the conventional method, where we need to fit the electro-magnetic field with an exponential decay that requires a relatively long data set. For a width-modulated line defect cavity that has a Q of 8.5 × 10(7) we obtained the same value as with a conventional method but with 94% less computation time.
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Simulação por Computador , Desenho Assistido por Computador , Nanotecnologia/instrumentação , Óptica e Fotônica/instrumentação , Fótons , Cristalização , Desenho de EquipamentoRESUMO
We design scalable all-optical logic gates that operate with the same input and output wavelength. We demonstrated the operation by using coupled mode equations, and investigated the impact of input power fluctuations and fabrication errors. We found that a wavelength fluctuation 0.3 times greater than the resonant wavelength width will degrade the operation of the system. Stronger coupling increases the wavelength tolerance. As regards coupling coefficient fluctuation, we found that the system is error-free when the fabrication precision is better than ± 5 nm. This study provides information on the required input power stability and tolerable fabrication errors of a scalable system, which moves the numerical study closer to practical realization.
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Comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) is a powerful tool for comprehensive analysis of organic pollutants. In this study, we developed a powerful analytical method using GC×GC for rapid and accurate identification and quantification of compounds in environmental samples with complex matrices. Specifically, we have developed an automatic peak sentinel tool, T-SEN, with free programming software, R. The tool, which consists of a simple algorithm for on peak finding and peak shape identification, allows rapid screening of target compounds, even for large data sets from GC×GC coupled to high resolution time of flight mass spectrometry (HRTOFMS). The software tool automatically assigns and quantifies compounds that are listed in user databases. T-SEN works on a typical 64 bit workstation, and the reference calculation speed is 10-20 min for approximately 170 compounds for peak finding (five ion count setting) and integration from 1-2GB of sample data acquired by GC×GC-HRTOFMS. We analyzed and quantified 17 PCDD/F congeners and 24 PCB congeners in a crude lake sediment extract by both GC×GC coupled to quadrupole mass spectrometry (qMS) and GC×GC-HRTOFMS with T-SEN. While GC×GC-qMS with T-SEN resulted in false identification and inaccurate quantification, GC×GC-HRTOFMS with T-SEN provided correct identification and accurate quantification of compounds without sample pre-treatment. The differences between the values measured by GC×GC-HRTOFMS with T-SEN and the certified values for the certified reference material ranged from 7.3 to 36.9% for compounds with concentrations above the limit of quantification. False positives/negatives were not observed, except for when co-elution occurred. The technique of GC×GC-HRTOFMS in combination with T-SEN provides rapid and accurate screening and represents a powerful new approach for comprehensive analysis.
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We developed a method that selectively extracts a subset from comprehensive 2D gas chromatography (GC×GC) and high-resolution time-of-flight mass spectrometry (HRTOFMS) data to detect and identify trace levels of organohalogens. The data were obtained by measuring several environmental and biological samples, namely fly ash, soil, sediment, the atmosphere, and human urine. For global analysis, some samples were measured without purification. By using our novel software, the mass spectra of organochlorines or organobromines were then extracted into a data subset under high mass accuracy conditions that were approximately equivalent to a mass resolution of 6000 for some samples. Mass defect filtering as pre-screening for the data extraction was very effective in removing the mass spectra of hydrocarbons. Those results showed that data obtained with HRTOFMS are valuable for global analysis of organohalogens, and probably of other compounds if specific data extraction methods can be devised.
Assuntos
Mineração de Dados/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Halogenados/análise , Hidrocarbonetos Halogenados/química , Software , Bases de Dados FactuaisRESUMO
We compared the effect of ambient temperature observed in two different seasons on the size distribution and particle number concentration (PNC) as a function of distance (up to ~250 m) from a major traffic road (25% of the vehicles are heavy-duty diesel vehicles). The modal particle diameter was found between 10 and 30 nm at the roadside in the winter. However, there was no peak for this size range in the summer, even at the roadside. Ambient temperature affects both the atmospheric dilution ratio (DR) and the evaporation rate of particles, thus it affects the decay rate of PNC. We corrected the DR effect in order to focus on the effect of particle evaporation on PNC decay. The decay rate of PNC with DR was found to depend on the season and particle diameter. During the winter, the decay rate for smaller particles (<30 nm) was much higher (i.e., the concentration decreased significantly against DR), whereas it was low during the summer. In contrast, for particles >30 nm in diameter, the decay rate was nearly the same during both seasons. This distinction between particles less than or greater than 30 nm in diameter reflects differences in particle volatility properties. Mass-transfer theory was used to estimate evaporation rates of C20-C36 n-alkane particles, which are the major n-alkanes in diesel exhaust particles. The C20-C28 n-alkanes of 30-nm particles completely evaporate at 31.2 °C (summer), and their lifetime is shorter than the transport time of air masses in our region of interest. Absence of the peak at 10-30 nm and the low decay rate of PNC <30 nm in diameter in the summer were likely due to the evaporation of compounds of similar volatilities comparable to the C20-C36 n-alkanes from particles near the exhaust pipes of vehicles, and complete evaporation of semivolatile materials before they reached the roadside. These results suggest that the lifetime of particles <30 nm in diameter depends on the ambient temperature, which differs between seasons. This leads us to conclude that these particles show distinctly different spatial distributions depending on the season.
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Atmosfera/química , Material Particulado/análise , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/química , Alcanos/química , Cidades , Exposição Ambiental , Monitoramento Ambiental/métodos , Japão , Modelos Químicos , Tamanho da Partícula , Estações do Ano , Temperatura , Emissões de Veículos/análise , Compostos Orgânicos Voláteis/químicaRESUMO
We developed a highly sensitive method for determination of polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated, nitrated, and methylated PAHs) in trace particulate samples by using thermal desorption followed by comprehensive two-dimensional gas chromatography coupled with tandem mass spectrometry (TD-GC×GC-MS/MS) with a selected reaction monitoring mode. The sensitivity of TD-GC×GC-MS/MS was greater than that of TD-GC-HRMS and TD-GC×GC-QMS by one or two orders of magnitude. The instrumental detection limits were 0.03-0.3pg (PAHs), 0.04-0.2pg (oxygenated PAHs), 0.03-0.1pg (nitrated PAHs), and 0.01-0.08pg (methylated PAHs). For small amounts (10-20µg) of standard reference materials (SRMs 1649a and 1650b, urban dust and diesel exhaust particles, respectively), the values measured by using TD-GC×GC-MS/MS agreed with the certified or reference values within a factor of two. Major analytes were quantified successfully by TD-GC×GC-MS/MS from diesel exhaust nanoparticles (18-32nm) and accumulation-mode particles (100-180nm) from an 8-L diesel engine with no exhaust after-treatment system. The PAH profiles differed among driving conditions but they did not differ markedly among the particle sizes.
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Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Policíclicos Aromáticos/análise , Calibragem , Limite de Detecção , Material Particulado/química , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/métodos , Emissões de Veículos/análiseRESUMO
A method for the determination of ultra-trace amounts of organochlorine pesticides (OCPs) in river water was developed by using stir bar sorptive extraction (SBSE) followed by thermal desorption and comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry (SBSE-TD-GC×GC-HRTOF-MS). SBSE conditions such as extraction time profiles, phase ratio (ß: sample volume/polydimethylsiloxane (PDMS) volume), and modifier addition, were examined. Fifty milli-liter sample including 10% acetone was extracted for 3 h using stir bars with a length of 20 mm and coated with a 0.5 mm layer of PDMS (PDMS volume, 47 µL). The stir bar was thermally desorbed and subsequently analyzed by GC×GC-HRTOF-MS. The method showed good linearity over the concentration range from 50 to 1000 pg L(-1) or 2000 pg L(-1) for all analytes, and the correlation coefficients (r(2)) were greater than 0.9903 (except for ß-HCH, r(2)=0.9870). The limit of detection (LOD) ranged from 10 to 44 pg L(-1). The method was successfully applied to the determination of 16 OCPs at pg L(-1) to ng L(-1) in river water. The results agree fairly well with the values obtained by a conventional liquid-liquid extraction (LLE)-GC-HRMS (selected ion monitoring: SIM) method using large sample volume (20 L). The method also allows screening of non-target compounds, e.g. pesticides and their degradation products, polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) and metabolites in the same river water sample, by using full spectrum acquisition with accurate mass in GC×GC.
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Fracionamento Químico/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Rios/química , Poluentes Químicos da Água/análise , Modelos Lineares , Hidrocarbonetos Policíclicos Aromáticos , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
The radiocarbon ((14)C) of total carbon (TC) in atmospheric fine particles was measured at 6 h or 12 h intervals at two sites, 50 and 100 km downwind from Tokyo, Japan (Kisai and Maebashi) in summer 2007. The percent modern carbon (pMC) showed clear diurnal variations with minimums in the daytime. The mean pMC values at Maebashi were 28 ± 7 in the daytime and 45 ± 16 at night (37 ± 15 for the overall period). Those at Kisai were 26 ± 9 in the daytime and 44 ± 8 at night (37 ± 12 for the overall period). This data indicates that fossil sources were major contributors to the daytime TC, while fossil and modern sources had comparable contributions to nighttime TC in the suburban areas. At both sites, the concentration of fossil carbon as well as O(3) and the estimated secondary organic carbon increased in the daytime. These results suggest that fossil sources around Tokyo contributed significantly to the high daytime concentration of secondary organic aerosols (SOA) at the two suburban sites. A comparison of pMC and the ratio of elemental carbon/TC from our particulate samples with those from three end-member sources corroborates the dominant role of fossil SOA in the daytime.
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Movimentos do Ar , Ritmo Circadiano , Material Particulado/análise , Estações do Ano , Carbono/análise , Radioisótopos de Carbono , Fósseis , Compostos Orgânicos/análise , Ozônio/análise , TóquioRESUMO
For accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in dust samples, we investigated the use of microwave-assisted solvent extraction (MAE) combined with isotope-dilution mass spectrometry (IDMS) using deuterium-labelled PAHs (D-PAHs). Although MAE with a methanol/toluene mixture (1:3 by volume) at 160°C for 40 min was best for extracting PAHs from tunnel dust among examined, the recovery yields of D-PAHs decreased with increasing molecular weight (<40% for MW≥264; that of deuterium-labelled indeno[123-cd]pyrene (D-IcdP) was only 7.1%). Although the residues were extracted a second time, the observed concentrations did not change dramatically (<5%), and the recovery yields of heavier D-PAHs (i.e., MW≥264) were approximately half of those of the first extract, including D-IcdP (3.4%). These results suggest that both partitioning and isotopic equilibria of PAHs and D-PAHs between sample and solvent were achieved for extractable heavier PAHs under the condition. Thus, the observed concentrations of PAHs obtained by MAE-IDMS were reasonable, even though recovery yields of D-PAHs were <50%. From the results of carbon analyses and extractable contents, lower recovery yields of D-PAHs from the tunnel dust were due to a large content of char with low extractable contents.
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We successfully detected halogenated compounds from several kinds of environmental samples by using a comprehensive two-dimensional gas chromatograph coupled with a tandem mass spectrometer (GC×GC-MS/MS). For the global detection of organohalogens, fly ash sample extracts were directly measured without any cleanup process. The global and selective detection of halogenated compounds was achieved by neutral loss scans of chlorine, bromine and/or fluorine using an MS/MS. It was also possible to search for and identify compounds using two-dimensional mass chromatograms and mass profiles obtained from measurements of the same sample with a GC×GC-high resolution time-of-flight mass spectrometer (HRTofMS) under the same conditions as those used for the GC×GC-MS/MS. In this study, novel software tools were also developed to help find target (halogenated) compounds in the data provided by a GC×GC-HRTofMS. As a result, many dioxin and polychlorinated biphenyl congeners and many other halogenated compounds were found in fly ash extract and sediment samples. By extracting the desired information, which concerned organohalogens in this study, from huge quantities of data with the GC×GC-HRTofMS, we reveal the possibility of realizing the total global detection of compounds with one GC measurement of a sample without any pre-treatment.
Assuntos
Dioxinas/análise , Poluentes Ambientais/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Aromáticos/análise , Espectrometria de Massas em Tandem/métodos , Carbono/química , Cinza de Carvão , Material Particulado/química , Bifenil Polibromatos , Bifenilos Policlorados , Hidrocarbonetos Policíclicos AromáticosRESUMO
Diurnal variations of fossil secondary organic carbon (SOC) and nonfossil SOC were determined for the first time using a combination of several carbonaceous aerosol measurement techniques, including radiocarbon (¹4C) determinations by accelerator mass spectrometry, and a receptor model (chemical mass balance, CMB) at a site downwind of Tokyo during the summer of 2007. Fossil SOC showed distinct diurnal variation with a maximum during daytime, whereas diurnal variation of nonfossil SOC was relatively small. This behavior was reproduced by a chemical transport model (CTM). However, the CTM underestimated the concentration of anthropogenic secondary organic aerosol (ASOA) by a factor of 4-7, suggesting that ASOA enhancement during daytime is not explained by production from volatile organic compounds that are traditionally considered major ASOA precursors. This result suggests that unidentified semivolatile organic compounds or multiphase chemistry may contribute largely to ASOA production. As our knowledge of production pathways of secondary organic aerosol (SOA) is still limited, diurnal variations of fossil and nonfossil SOC in our estimate give an important experimental constraint for future development of SOA models.
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Aerossóis/análise , Poluentes Atmosféricos/análise , Carbono/análise , Combustíveis Fósseis/análise , Aerossóis/química , Movimentos do Ar , Poluentes Atmosféricos/química , Carbono/química , Ritmo Circadiano , Cidades , Monitoramento Ambiental/métodos , Japão , Cinética , Modelos QuímicosRESUMO
Atmospheric nanoparticles (<0.050 microm) have caused great concern recently due to their potential to affect human health. However, little is known about the chemical composition, sources, and atmospheric behavior of atmospheric nanoparticles. Although gas chromatography/mass spectrometry (GC/MS) after solvent extraction is a commonly used and powerful method for the identification of nonpolar organic compounds in particles, solvent-extraction methods are difficult to apply to nanoparticles because nanoparticles are present in small masses in spite of their high number concentrations. Therefore, we made an attempt to apply thermal desorption-GC/MS (TD-GC/MS), which was expected to be more sensitive than solvent-extraction methods, to atmospheric nanoparticles. A commercial pyrolyzer was used for TD. Prior to the application, the optimum TD-GC/MS conditions for atmospheric particles and diesel exhaust particles (DEP) collected on filters were investigated. Various TD parameters, including desorption time and temperature, were investigated using these test samples and a n-alkanes standard solution. The optimum TD conditions were as follows: ramped desorption from 50 degrees C to 450 degrees C at 50 degrees C min(-1) and then hold for 2 min. Desorption was incomplete at temperatures of 250 degrees C or lower, and considerable pyrolysis occurred at temperatures of 550 degrees C or higher. The TD-GC/MS performance, including the linearity of the calibration curves, repeatability, detection and quantification limits, and sample recovery, under the optimized conditions was evaluated for n-alkanes. It was found that the TD-GC/MS could be applied to extremely small amount of particles (e.g., 5 microg for DEP). The TD-GC/MS was applied to the size-resolved particles, including the nanoparticle fraction (0.0290-0.0580 microm), from roadside atmosphere, and the concentrations of C18-C33 n-alkanes in the particles were determined. The chromatogram pattern of the roadside 0.102-0.163 microm (major size range for DEP) particles was similar to that of the DEP sample. The chromatogram pattern of the roadside nanoparticles was similar to that of diesel lubricating oil, although the proportion of less volatile compounds was slightly larger in the nanoparticles. It is suggested that lubricating oil strongly contributed to the nonpolar organic composition of the roadside nanoparticles, and that more volatile organic compounds in the nanoparticles evaporated in the atmosphere. It was shown that the TD-GC/MS is effective for characterization of atmospheric nanoparticles.
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Atmosfera/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Nanopartículas/análise , Material Particulado/análise , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Emissões de Veículos/análise , Monitoramento Ambiental/métodos , Temperatura Alta , Microquímica/métodos , Veículos Automotores , Nanopartículas/químicaRESUMO
A method is described for characterization of size-resolved particles including the nanoparticles fraction with a diameter of 29-58 nm in roadside atmosphere. The method is based on thermal desorption (TD) of a sample followed by comprehensive two-dimensional gas chromatography (GC x GC) with novel detection capabilities, including high resolution time-of-flight mass spectrometry (HRTOF-MS) and simultaneous detection with a nitrogen phosphorous detector (NPD) and a quadrupole mass spectrometer (qMS). Increased selectivity with the GC x GC-HRTOF-MS allows a group type separation of a selected chemical class, e.g. oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs), using mass chromatography with a 0.05 Da wide window in the complex sample matrix. Also, exact mass measurements provide candidate elemental compositions as well as NIST library search results for tentative identifications of 50 compounds. Moreover, the simultaneous detection with the NPD and the qMS elucidate the presence of 15 nitrogen-containing compounds. Quantitative analysis of selected PAHs in several size-resolved particles was also performed by use of the TD-GC x GC-qMS with limited scan range. The method showed good linearity (r2>0.988) and high sensitivity (limit of quantification: <10 pg) for most of the target PAHs. The concentration of PAHs per particulate matter (PM) mass in nanoparticles was considerably higher than those of larger size of particles with a diameter of >102 nm.
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Atmosfera/análise , Cromatografia Gasosa/métodos , Espectrometria de Massas/métodos , Nanopartículas/análise , Atmosfera/química , Nanopartículas/química , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/química , Reprodutibilidade dos TestesRESUMO
The time course of ambient benzene level and benzene discharge was investigated. Data obtained by continuous monitoring and monthly monitoring showed a decreasing trend of ambient benzene level. The rate of decrease was around 22-25% per two years from FY 1997 to FY 1999. The discharge data of benzene reported by several organizations were collected and re-arranged to estimate the total discharge in Japan. The total amount of benzene discharged decreased by 25% from 1997 to 1999. Risk reduction due to the regulation of benzene content in gasoline as predicted in our previous report was verified by the obtained data.