Source apportionment of anthropogenic and biogenic organic aerosol over the Tokyo metropolitan area from forward and receptor models.

Organic aerosol (OA) is a dominant component of PM2.5, and accurate knowledge of its sources is critical for identification of cost-effective measures to reduce PM2.5. For accurate source apportionment of OA, we conducted field measurements of organic tracers at three sites (one urban, one suburban, and one forest) in the Tokyo Metropolitan Area and numerical simulations of forward and receptor models. We estimated the source contributions of OA by calculating three receptor models (positive matrix factorization, chemical mass balance, and secondary organic aerosol (SOA)-tracer method) using the ambient concentrations, source profiles, and production yields of OA tracers. Sensitivity simulations of the forward model (chemical transport model) for precursor emissions and SOA formation pathways were conducted. Cross-validation between the receptor and forward models demonstrated that biogenic and anthropogenic SOA were better reproduced by the forward model with updated modules for emissions of biogenic volatile organic compounds (VOC) and for SOA formation from biogenic VOC and intermediate-volatility organic compounds than by the default setup. The source contributions estimated by the forward model generally agreed with those of the receptor models for the major OA sources: mobile sources, biomass combustion, biogenic SOA, and anthropogenic SOA. The contributions of anthropogenic SOA, which are the main focus of this study, were estimated by the forward and receptor models to have been between 9 % and 15 % in summer 2019. The observed percent modern carbon data indicate that the amounts of anthropogenic SOA produced during daytime have substantially declined from 2007 to 2019. This trend is consistent with the decreasing trend of anthropogenic VOC, suggesting that reduction of anthropogenic VOC has been effective in reducing anthropogenic SOA in the atmosphere.

Application of inert gas-mediated ionization for qualitative screening of chlorinated aromatics in house dust by comprehensive two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry.

The development of highly selective and sensitive analytical methods for the nontarget screening of persistent organic pollutants such as halogenated compounds in environmental samples is a challenging task. Soft ionization mass spectrometry has emerged as a powerful technique for obtaining essential molecular information, and it is expected to reveal compounds that remain hidden with conventional fragmentation techniques such as electron ionization (EI). In this study, a soft ionization method based on electron capture negative ionization using an inert gas was developed for the nontarget screening of chlorinated aromatics in environmental samples and was applied to comprehensive two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (GC × GC-HRToFMS). In particular, argon (Ar) and helium (He) were evaluated as inert moderating gases, and were compared against the conventional methane (CH4). The optimal ionization conditions, including the flow rate and ion source temperature, were investigated based on the molecular ion intensities of highly chlorinated aromatics decachlorobiphenyl and octachlorodibenzofuran. Ar-mediated soft ionization provided the best sensitivity to molecular ions among the three gases at a low flow rate (0.1 mL min-1) and low ion source temperature, and more selective detection of molecular ions (i.e., less fragmentation) was obtained with the inert gases than with CH4. This method is also applicable to other chlorinated aromatics such as tetra- to nonachlorobiphenyls, tetra- to heptachlorinated dibenzofurans, pentachlorobenzene, and hexachlorobenzene. To demonstrate the applicability of the proposed method to a wide range of chlorinated aromatics in environmental samples, both Ar-mediated soft ionization and conventional EI were applied to GC × GC-HRToFMS for analysis of a crude extract of house dust. Soft ionization enabled the selective and sensitive detection of molecular ions for minor amounts of chlorinated aromatics, even in complex matrices. Furthermore, the extracted ion chromatograms of halide anions (Cl- or Br-) were useful for screening other chlorinated or brominated compounds in the environmental samples. The results suggest that combining information on halide anions obtained by soft ionization and the structural information provided by EI would constitute a powerful approach for the comprehensive identification of chlorinated aromatics.

Volatility Distribution of Organic Compounds in Sewage Incineration Emissions.

Intermediate volatility and semivolatile organic compounds (IVOC/SVOC) are important precursors of secondary organic aerosol (SOA) while SVOC is an important contributor to primary organic aerosol (POA). However, combustion emissions data for volatility classes are limited. This study reports the gas and particle emissions that were sampled with various dilution factors from a sewage sludge incinerator burning fuel oil. Volatility distributions were determined using measurements from online mass spectrometry and offline organic compound analyses. In the low volatility organic compound (LVOC) to IVOC range, volatility bins with organic saturation concentrations of 10-100 µg m-3 were most abundant, which was due to organic acids generated from sludge burning. Organic aerosol (OA) emission factors (EFOA) increased 1.4 times after cooling to ambient temperatures in comparison to those of the samples from the hot stack. Upon further isothermal dilution at 25 °C, the EFOA decreased while organic gas phase EFs increased with increasing dilution. Phase partitioning in volatility bins with saturation concentrations of 10-100 µg m-3 was sensitive to isothermal dilution that influenced the EFs. Therefore, gas- and particle-phase measurements alone cannot constrain EFs for these volatility classes. Low dilution factors may overestimate the particle phase and underestimate the gas phase EFs compared with real-world emission conditions.

Contributions of Condensable Particulate Matter to Atmospheric Organic Aerosol over Japan.

Because emission rates of particulate matter (PM) from stationary combustion sources have been measured without dilution or cooling in Japan, condensable PM has not been included in Japanese emission inventories. In this study, we modified an emission inventory to include condensable PM from stationary combustion sources based on the recent emission surveys using a dilution method. As a result, emission rates of organic aerosol (OA) increased by a factor of 7 over Japan. Stationary combustion sources in the industrial and energy sectors became the largest contributors to OA emissions over Japan in the revised estimates (filterable-plus-condensable PM), while road transport and biomass burning were the dominant OA sources in the previous estimate (filterable PM). These results indicate that condensable PM from large combustion sources makes critical contributions to total PM2.5 emissions. Simulated contributions of condensable PM from combustion sources to atmospheric OA drastically increased around urban and industrial areas, including the Kanto region, where OA concentrations increased by factors of 2.5-6.1. Consideration of condensable PM from stationary combustion sources improved model estimates of OA in winter but caused overestimation of OA concentrations in summer. Contributions of primary and secondary OA should be further evaluated by comparing with organic tracer measurements.

Selective and comprehensive analysis of organohalogen compounds by GC × GC-HRTofMS and MS/MS.

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.

Sensitivities of Simulated Source Contributions and Health Impacts of PM2.5 to Aerosol Models.

Chemical transport models are useful tools for evaluating source contributions and health impacts of PM2.5 in the atmosphere. We recently found that concentrations of PM2.5 compounds over Japan were much better reproduced by a volatility basis set model with an enhanced dry deposition velocity of HNO3 and NH3 compared with a two-product yield model. In this study, we evaluated the sensitivities to organic aerosol models of the simulated source contributions to PM2.5 concentrations and of PM2.5-related mortality. Overall, the simulated source contributions to PM2.5 were similar between the two models. However, because of the improvements associated with the volatility basis set model, the contributions of ammonia sources decreased, particularly in winter and spring, and contributions of biogenic and stationary evaporative sources increased in spring and summer. The improved model estimated that emission sources in Japan contributed 35%-48% of the PM2.5-related mortality in Japan. These values were higher than the domestic contributions to average PM2.5 concentrations in Japan (26%-33%) because the domestic contributions were higher in higher population areas. These results indicate that control of both domestic and foreign emissions is necessary to reduce health impacts due to PM2.5 in Japan.

Nontarget approach for environmental monitoring by GC × GC-HRTOFMS in the Tokyo Bay basin.

In this study, we developed an approach for sequential nontarget and target screening for the rapid and efficient analysis of multiple samples as an environmental monitoring using a comprehensive two-dimensional gas chromatograph coupled to a high resolution time-of-flight mass spectrometer (GC × GC-HRTOFMS). A key feature of the approach was the construction of an accurate mass spectral database learned from the sample via nontarget screening. To enhance the detection power in the nontarget screening, a global spectral deconvolution procedure based on non-negative matrix factorization was applied. The approach was applied to the monitoring of rivers in the Tokyo Bay basin. The majority of the compounds detected by the nontarget screening were alkyl chain-based compounds (55%). In the quantitative target screening based on the output from the nontarget screening, particularly high levels of organophosphorus flame retardants (median concentrations of 31, 116 and 141 ng l(-1) for TDCPP, TCIPP and TBEP, respectively) were observed among the target compounds. Flame retardants used for household furniture and building materials were detected in river basins where buildings and arterial traffic were dominated. The developed GC × GC-HRTOFMS approach was efficient and effective for environmental monitoring and provided valuable new information on various aspects of monitoring in the context of environmental management.

Global spectral deconvolution based on non-negative matrix factorization in GC × GC-HRTOFMS.

A global spectral deconvolution, based on non-negative matrix factorization (NMF) in comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry, was developed. We evaluated the ability of various instrumental parameters and NMF settings to derive high-performance detection in nontarget screening using a sediment sample. To evaluate the performance of the process, a NIST library search was used to identify the deconvoluted spectra. Differences of the instrumental scan rates (25 and 50 Hz) in deconvolution were evaluated and results show that a high scan rate enhanced the number of compounds detected in the sediment sample. A higher mass resolution in the range of 1,000 to 10,000 and a higher m/z precision in the deconvolution were needed to obtain an accurate mass database. After removal of multiple duplicate hits, which occurred in batch processes of NIST library search on the deconvolution result, 62 unique assignable spectra with a match factor ≥900 were obtained in the deconvoluted chromatogram from the sediment sample, including 54 spectra that were refined by the deconvolution. This method will help to detect and build up well-resolved reference spectra from various complex mixtures and will accelerate nontarget screening.

Retrospective analysis by data processing tools for comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry: a challenge for matrix-rich sediment core sample from Tokyo Bay.

Data processing tools for non-target analysis using comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRTOFMS) were developed and applied to a sediment core in Tokyo Bay, focusing on chlorinated compounds in this study. The processing tools were classified in two different methods: (1) the consecutive use of mass defect filter followed by artificial neutral loss scan (MDF/artificial NLS) as a qualitative non-target screening method and (2) Entire Domain Combined Spectra Extraction and Integration Program (ComSpec) and two-dimensional peak sentinel (T-SEN) as a semi-quantitative target screening method. MDF/artificial NLS as a non-target screening approach revealed that PCBs, followed by octachlorodibenzo dioxin (OCDD), were the main chlorinated compounds present in all sediment layers. Furthermore, unknown peaks thought to be chlorinated compounds were found in increasing numbers, some in increasing amounts. T-SEN and ComSpec as a target screening approach were adapted for automatic semi-quantitative analysis showed that, in decreasing concentration order, PCBs, OCDD, and dichlorodiphenyltrichloroethane and its metabolites (DDEs, DDDs) were the main chlorinated pollutants in the sediments. The complementary use of both techniques allows us to extract significant chlorinated pollutants, including non-targeted compounds. This retrospective analysis by this approach performed well even on matrix-rich sediment samples and provided us an interesting insight of historical trends of pollution in Tokyo Bay.

Rapid automatic identification and quantification of compounds in complex matrices using comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry with a peak sentinel tool.

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.

Selective extraction of halogenated compounds from data measured by comprehensive multidimensional gas chromatography/high resolution time-of-flight mass spectrometry for non-target analysis of environmental and biological samples.

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.

Seasonal differences of the atmospheric particle size distribution in a metropolitan area in Japan.

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.

Thermal desorption - comprehensive two-dimensional gas chromatography coupled with tandem mass spectrometry for determination of trace polycyclic aromatic hydrocarbons and their derivatives.

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.

Stir bar sorptive extraction and comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry for ultra-trace analysis of organochlorine pesticides in river water.

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.

Radiocarbon (14C) diurnal variations in fine particles at sites downwind from Tokyo, Japan in summer.

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.

Global and selective detection of organohalogens in environmental samples by comprehensive two-dimensional gas chromatography-tandem mass spectrometry and high-resolution time-of-flight mass spectrometry.

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.

An association between long-term exposure to ambient air pollution and mortality from lung cancer and respiratory diseases in Japan.

BACKGROUND: Evidence for a link between long-term exposure to air pollution and lung cancer is limited to Western populations. In this prospective cohort study, we examined this association in a Japanese population. METHODS: The study comprised 63 520 participants living in 6 areas in 3 Japanese prefectures who were enrolled between 1983 and 1985. Exposure to particulate matter less than 2.5 µm in aerodynamic diameter (PM(2.5)), sulfur dioxide (SO(2)), and nitrogen dioxide (NO(2)) was assessed using data from monitoring stations located in or nearby each area. The Cox proportional hazards model was used to calculate the hazard ratios associated with the average concentrations of these air pollutants. RESULTS: The 10-year average concentrations of PM(2.5), SO(2), and NO(2) before recruitment (1974-1983) were 16.8 to 41.9 µg/m(3), 2.4 to 19.0 ppb, and 1.2 to 33.7 ppb, respectively (inter-area range). During an average follow-up of 8.7 years, there were 6687 deaths, including 518 deaths from lung cancer. The hazard ratios for lung cancer mortality associated with a 10-unit increase in PM(2.5) (µg/m(3)), SO(2) (ppb), and NO(2) (ppb) were 1.24 (95% confidence interval: 1.12-1.37), 1.26 (1.07-1.48), and 1.17 (1.10-1.26), respectively, after adjustment for tobacco smoking and other confounding factors. In addition, a significant increase in risk was observed for male smokers and female never smokers. Respiratory diseases, particularly pneumonia, were also significantly associated with all the air pollutants. CONCLUSIONS: Long-term exposure to air pollution is associated with lung cancer and respiratory diseases in Japan.

Contrasting diurnal variations in fossil and nonfossil secondary organic aerosol in urban outflow, Japan.

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.

Characterization of dilution conditions for diesel nanoparticle inhalation studies.

Diesel exhaust nanoparticles easily coagulate during transportation from the engine to the inhalation chamber, depending on concentrations and residence times. Although dilution is effective in suppressing coagulation growth of nanoparticles, volatile organic carbon (OC) evaporates as a result of dilution. Thus, the design of an inhalation facility to investigate the health effects of nanoparticle-rich exhaust is important. In this study, we determined the optimum dilution conditions in consideration of coagulation growth and evaporation of OC for inhalation studies of nanoparticle-rich diesel exhaust. We found that a short residence time prevented coagulation growth in the primary dilution tunnel after the primary dilution or before the diluted exhaust reached the inhalation chamber after the secondary dilution. However, due to the longer residence time in the inhalation chamber, the coagulation growth occurred in the inhalation chamber depending on secondary dilution ratio which controlled exposure dose (particle concentration in the inhalation chamber). We determined that the secondary dilution ratio for the high-concentration chamber should be around 4.5 times to prevent coagulation growth and to obtain the desired exposure dose. We also found that the loss of OC was relatively independent of the secondary dilution ratio when the secondary dilution ratio was more than 10 times because it seemed to reach a gas-particle equilibrium in the inhalation chamber. We therefore set the secondary dilution ratios for the middle- and low-concentration chambers to 13.5 and 40.5 times, respectively.

Comparison of carbonaceous aerosols in Tokyo before and after implementation of diesel exhaust restrictions.

We compared the status of carbonaceous aerosols in Tokyo before and after the implementation of a diesel vehicle regulation intended to reduce the quantity of particulate carbon from diesel engines in one of the largest scale ever attempts at vehicle exhaust control. Radiocarbon (14C) in elemental carbon (EC) and total carbon (TC) were analyzed to identify fossil fuel carbonaceous particles emitted from diesel-powered vehicles. One-sided paired-month t-tests showed no distinct difference in the absolute concentrations of particles in terms of total mass (19.5 to 18.0 microg m(-3); p = 0.321), EC (3.6 to 3.3 microg m(-3); p = 0.272), and TC (6.3 to 6.2 microg m(-3); p = 0.418) for the finest particles (d(a) < 1.1 microm) after the implementation of the regulation. The ratios of the concentrations of the chemical constituents were, however, altered after the regulation. EC/TC was significantly decreased from 56.7% to 50.2% (p = 0.039). Although it was not statistically significant, the percentage of fossil carbon in EC also decreased (67.8% to 63.8%; p = 0.104). Since EC is predominantly of combustion origin, the observed decrease was likely due to the decrease in fossil EC emissions from diesel-powered vehicles. The decrease in EC/TC after the implementation of the regulation was also likely to have resulted from attachment to diesel vehicle exhaust systems of particulate filters as required as part of the regulation by the Tokyo Metropolitan Government. The EC/TC of fossil carbon of the finest particles decreased from 66.2% to 55.2% (p = 0.066), but EC/TC of biomass carbon did not decrease but rose slightly from 43.6% to 44.5% (p > 0.5). Thus, the relative ratios of components of carbonaceous aerosol particles, such as 14C, could provide a better understanding of the atmospheric pollution status, despite short-term fluctuations, than do measurements of absolute concentrations.