Bias in Filter-Based Aerosol Light Absorption Measurements Due to Organic Aerosol Loading: Evidence from Laboratory Measurements

Light absorption by soot or nigrosin dye aerosol particles were measured in the laboratory using a particle soot absorption photometer (PSAP) and a photo-acoustic spectrometer (PAS) to assess the influence of non-absorbing organic aerosol (OA) on the PSAP measurements. For the PSAP, particle light absorption is measured after collection on a filter, whereas for the PAS light absorption is measured while the particles remain suspended in the gas phase. OA was generated from the reaction of α -pinene with ozone. It was observed that the presence of this OA in an external mixture of absorbing aerosol and OA can cause an increase in the light absorption measured by the PSAP, relative to that measured by the PAS, by more than a factor of two. This enhancement in the PSAP absorption was found to increase as the amount of OA increased relative to the absorbing compound. Additionally, experiments where absorbing aerosol was deposited on a PSAP filter prior to addition of OA demonstrated that the non-absorbing OA can actually appear as if it were absorbing, with measured single scattering albedo values as low as 0.92. These results indicate that filter-based measurement techniques may significantly overestimate light absorption by aerosols in the atmosphere under conditions where the organic loading is large, with consequent implications for understanding and calculating the Earth's radiation budget. These laboratory experiments aid in the interpretation of results from a recent field study, discussed in a companion article (Lack et al. 2008 Lack, D. A., Cappa, C. D., Baynard, T., Massoli, P., Covert, D. S., Sierau, B., Bates, T. S., Quinn, P. K., Lovejoy, E. R. and Ravishankara, A. R. 2008. Bias in Filter-Based Aerosol Absorption Measurements Due to Organic Aerosol Loading: Evidence from Ambient Measurements. Aerosol Sci. and Technol., 42: 1033–1041. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]).     

Mechanical Effect of Acetic Acid Lignin Adsorption on Honeycomb-Patterned Cellulosic Films

Abstract

We have already fabricated honeycomb-patterned cellulosic films with cellulose I and II polymorphisms as a basal framework in order to create an artificial woody cell wall.^{[ 1} Nemoto, J., Uraki, Y., Kishimoto, T., Sano, Y., Funada, R., Obata, N., Yabu, H., Tanaka, M. and Shimomura, M. 2005. Production of mesocopically patterned cellulose film. Bioresour. Technol., 96: 1955–1958.  [Google Scholar] ^{, 2} Uraki, Y., Nemoto, J., Otsuka, H., Tamai, Y., Sugiyama, J., Kishimoto, T., Ubukata, M., Yabu, H., Tanaka, M. and Shimomura, M. 2007. Honeycomb-like architecture produced by living bacteria, Gluconacetobacter xylinus. Carbohydr. Polym., 69: 1–6. [Crossref], [Web of Science ®] , [Google Scholar] ^] The adsorption of an isolated lignin, acetic acid lignin (AL), was attempted onto the honeycomb films not only to develop materials further mimicking the cell wall but also to elucidate the mechanical effect of isolated lignin on the tensile strength of the cellulosic architecture. The tensile strengths of honeycomb-patterned cellulosic films were improved by the AL adsorption. Although the cellulosic films without lignin weakened under high moisture content conditions as compared with those under the low content conditions, the lignin-adsorbed cellulosic film maintained significant tensile strength even under the high content conditions. This result suggests that lignin contributes to reinforce the mechanical strength of cellulose framework, in particular high moisture conditions.     

Theory of Multi-Nozzle Impactor Stages and the Interpretation of Stage Mensuration Data

We describe a general theory of multi-nozzle cascade impactor stages and show how testers of inhaled drug products, such as metered-dose or dry-powder inhalers, can decide, solely from the stage nozzle dimensions, whether any used impactor is satisfactorily operating within its expected aerodynamic performance range. We first account for the realistic shape of particle collection efficiency curves and show that the effective diameter, described by Roberts and Romay (2005) Roberts D. L.Romay F. J.Relationship of Stage Mensuration Data to the Performance of New and Used Cascade ImpactorsJ. Aerosol Med2005184396–413[Crossref], [PubMed] , [Google Scholar], is sufficiently accurate as the primary indication of the aerodynamic performance.

To ensure that a used impactor is performing in the same aerodynamic range allowed for new impactors, one must also satisfy the other, more secondary factors of cascade impaction aerodynamics, most notably the distance to the collection surface relative to the nozzle diameter. We show what this constraint means in practice for used Next Generation Impactors (NGIs; Marple et al. 2003a Marple V. A.Roberts D. L.Romay F. J.Miller N. C.Truman K. G.Van Oort M.Olsson B.Holroyd M. J.Mitchell J. P.Hochrainer D.Next Generation Pharmaceutical Impactor, Part I: DesignJ. Aerosol Med2003a16283–299[Crossref], [PubMed] , [Google Scholar], b Marple V. A.Olson B. A.Santhanakrishnan K.Mitchell J. P.Murray S. C.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor—Part II: Archival CalibrationJ. Aerosol Med2003b16[Crossref], [PubMed] , [Google Scholar]; 2004 Marple V. A.Olson B. A.Santhanakrishnan K.Roberts D. L.Mitchell J. P.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor: A New Impactor for Pharmaceutical Inhaler Testing. Part III. Extension of Archival Calibration to 15 L/minJ. Aerosol Med200417335–343[Crossref], [PubMed] , [Google Scholar]), and show that partially occluded nozzles are the most likely nozzles to fail this test.

Applying this principle that used impactors should perform in the same aerodynamic range as new impactors, we derive constraints on the nozzle diameters of any used NGI (Table 6, main text). We can partially apply this principle to other common impactors used for inhaler testing, such as the Andersen and the Marple-Miller, but are hindered by the absence of a published acceptable range for the distance to the impaction collection surface and by the limited published information on the shape of their stage collection efficiency curves.     

Quantification of Carboxylic and Carbonyl Functional Groups in Organic Aerosol Infrared Absorbance Spectra

Atmospheric aerosols are one of the least understood components of the climate system and incur adverse health effects on susceptible populations. Organic aerosols can make up as much as 80% of atmospheric aerosols (Lim and Turpin 2002 Lim, H. J. and Turpin, B. J. 2002. Origins of Primary and Secondary Organic Aerosol in Atlanta: Results’ of Time-Resolved Measurements During the Atlanta supersite experiment. Environ. Sci. Technol., 36: 4489–4496. 10.1021/es0206487[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]), and so its quantification and characterization plays an important role in reducing our uncertainty with regards to aerosol impacts on health and climate. As the number of organic molecules in the atmosphere are diverse in number (Hamilton et al. 2004 Hamilton, J. F., Webb, P. J., Lewis, A. C., Hopkins, J. R., Smith, S. and Davy, P. 2004. Partially Oxidised Organic Components in Urban Aerosol using GCXGC-TOF/MS. Atmos. Chem. Phys., 4: 1279–1290. [Crossref], [Web of Science ®] , [Google Scholar]), we advance a functional group representation of organic molecules as measured by Fourier transform infrared spectroscopy (FTIR) to characterize the chemical composition of particle samples. This study describes and evaluates the algorithm introduced by Russell et al. (2009 Russell, L. M., Takahama, S., Liu, S., Hawkins, L. N., Covert, D. S.Quinn, P. K. 2009. Oxygenated Fraction and Mass of Organic Aerosol from Direct Emission and Atmospheric Processing Measured on the R/V Ronald Brown During TEXAQS/GoMACCS 2006. J. Geophys. Res.-Atmos., 114: D00F05 10.1029/2008JD011275[Crossref], [Web of Science ®] , [Google Scholar]) for apportionment and quantification of oxygenated (carbonyl and hydroxyl) functional groups from infrared absorption spectra. Molar absorptivities for carbonyl and hydroxyl bonds in carboxylic groups are obtained for several dicarboxylic compounds, and applied to a multifunctional compound and mixture to demonstrate the applicability of this method for more complex samples. Furthermore, functional group abundances of two aldehydic compounds, 2-deoxy-d-ribose and glyceraldehyde, atomized from aqueous solution are in quantitative agreement with number of bonds predicted after transformation of these compounds into diols. The procedure for spectra interpretation and quantitative analysis is described through the context of an algorithm in which contributions of background and analyte absorption to the infrared spectrum are apportioned by the superposition of lineshapes constrained by laboratory measurements.

Copyright 2013 American Association for Aerosol Research     

Numerical Evaluation of the Transfer Function of a Low Pressure DMA by Using the Langevin Dynamic Equation

The effect of Brownian diffusive particle trajectory of nanoparticles on the transfer function of the low pressure Differential Mobility Analyzer (LPDMA) was evaluated by a numerical simulation of the Langevin dynamic equation. The results of the simulation were compared with previously reported experimental results (Seto et al. 1997 Seto, T., Nakamoto, T., Okuyama, K., Adachi, M., Kuga, Y. and Takeuchi, K. 1997. Size Distribution Measurement of Nanometer-Sized Aerosol Particles using DMA under Low-Pressure Conditions. J. Aerosol Sci., 28: 193–206. [CROSSREF][Crossref] , [Google Scholar]; Seol et al. 2000 Seol, K. S., Tsutatani, Y., Camata, R. P., Yabumoto, J., Isomura, S., Okada, Y., Okuyama, K. and Takeuchi, K. 2000. A Differential Mobility Analyzer and A Faraday Cup Electrometer for Operation at 200-930 Pa Pressure. J. Aerosol Sci., 31: 1389–1395. [CSA][CROSSREF][Crossref] , [Google Scholar]) and Stolzenburg's transfer function (1988). As the operational pressure decreased, the peak and FWHM (full width of the transfer function at half of its maximum) values of transfer function, as calculated by numerical simulation, were increased, which was not evident from Stolzenburg's transfer function. In comparison with the experiments of Seto et al., discrepancies in the higher electrical mobility regime than from central mobility were found, which could be caused by the incomplete flow control of their LPDMA. However, the transfer function, as calculated by numerical simulation was in good agreement with experimental results reported by Seol et al., performed with the improved LPDMA at well-controlled operation conditions.     

Development of an Aerosol Dynamics Model for Dry Deposition Process Using the Moment Method

An aerosol dynamics model for dry deposition process is developed based on the moment method. Since it is hard to fully apply the moment method to the widely used dry deposition velocity expressions based on the resistance theory, the dry deposition velocity expression by Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] is used. Detailed deposition mechanisms such as Brownian diffusion, gravitational settling, and impaction are considered in the expression. To verify the validity of the derived dynamic equation, aerosol dynamics for the dry deposition process is estimated with the expressions of Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar], of Wesely (1989) Wesely, M. L. 1989. Parameterizations of Surface Resistance to Gaseous Dry Deposition in Regional-Scale, Numerical Models. Atmos. Environ., 23: 1293–1304. [Crossref], [Web of Science ®] , [Google Scholar] modified for particles (Seinfeld and Pandis 1998 Seinfeld, J. H. and Pandis, S. N. 1998. Atmospheric Chemistry and Physics, 958–996. New York, , USA: Wiley.  [Google Scholar]), in CMAQ, and with constant value used in RAINS-ASIA. Those expressions give different dynamics. Generally, the result for this study is between the result of modified Wesely's expression and CMAQ. When using the modified Wesely's expression with the number of sections being equal or smaller than 10, the resultant size distribution does not give the peak shape accurately.     

Selective Deflection and Localization of Flowing Aerosols onto a Substrate

Pulsed airflow cued by the fluorescence spectrum of a particular aerosol can be used to distinguish and deflect particles of biological origin out of an aerosol stream, permitting concentration of these particles for subsequent analysis (Pan et al. 2004 Pan, Y. L., Boutou, V., Bottiger, J. R., Zhang, S. S., Wolf, J. P. and Chang, R. K. 2004. A Puff of Air Sorts Bioaerosols for Pathogen Identification. Aerosol Sci. Technol., 38: 598–602. [CROSSREF][CSA][Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). However, these high velocity pulses of air have an inherent tendency to scatter particles, confounding efforts to concentrate these deflected particles for analysis. The ability to concentrate large numbers of biological particles into a small area on a collection substrate is particularly important for more species-specific techniques such as Raman and FTIR (Fourier Transform Infra-Red) spectroscopy, which require long integration times due to their weak signal strength. In the present work, a simple method is developed for deflecting and localizing particles after classification by a pulsed airflow. The concept is both modeled and experimentally tested. A specially designed funnel is used to localize the scattered particles onto an area of substrate as small as 1 mm in diameter. Computational fluid dynamics simulations were performed to investigate the interaction of the pulsed airflow with the deflected particles and the localizing funnel, in order to gain insight into design parameters and operating conditions that affect the efficiency of this technique. The results show that the combination of pulsed airflow with a localizing funnel effectively deflects and localizes the concentrated bioaerosol onto a small area of substrate or an opening of a microfluidic cell.     

Consistency and Traceability of Black Carbon Measurements Made by Laser-Induced Incandescence,Thermal-Optical Transmittance,and Filter-Based Photo-Absorption Techniques

In this study, we show that black carbon (BC) mass concentrations measured by different techniques are consistent and traceable. First, we present the volatilities of 13 organic compounds passed through a heated inlet. These data were used to quantify the interference of organic aerosols on the BC measurement techniques. The masses of the refractory particles that incandesce (m*_ref) were used to calibrate BC mass measured by a single-particle soot photometer (SP2), which uses laser-induced incandescence. This calibration was influenced little by refractory organics and agreed well with that of fullerene soot, which indicates the consistency of the standards. We estimated the interference of pyrolyzed refractory organics on the BC measured with a filter-based absorption photometer continuous soot monitoring system (COSMOS) with a heated inlet to be small in Asia. This was also confirmed by the stable mass absorption cross section (MAC) obtained by the high correlations between BC mass concentrations measured by COSMOS (M _COSMOS) and those measured by the thermal-optical transmittance method (M _TOT) (Kondo et al. 2009 Kondo, Y., Sahu, L., Kuwata, M., Miyazaki, Y., Takegawa, N., Moteki, N., Imaru, J., Han, S., Nakayama, T., Hu, M., Kim, Y. J. and Kita, K. 2009. Stabilization of the Mass Absorption Cross Section of Black Carbon for Filter-Based Absorption Photometry by the Use of a Heated Inlet. Aerosol Sci. Technol., 43: 741–756. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). M _COSMOS was also compared with total BC mass concentrations measured with an SP2 (M _SP2) in Tokyo in 2009. M _COSMOS and M _SP2 were highly correlated (r ²= 0.97) and agreed to within about 10% on average. These results demonstrate that M _SP2, M _COSMOS, and M _TOT were nearly identical. Use of the masses of incandescing refractory BC particles for calibration of BC mass concentrations determined by different techniques gave consistent results.     

Influence of Humidity on Clogging of Flat and Pleated HEPA Filters

The influence of humidity on changes to the pressure drop of flat and pleated HEPA filters clogged by polydisperse hygroscopic and non-hygroscopic aerosols has been studied. For flat filters, the results confirm the observations reported by Gupta et al. (1993) Gupta, A., Novick, V. J., Biswas, P. and Monson, P. R. 1993. Effect of Humidity and Particle Hygroscopicity on the Mass Loading Capacity of High Efficiency Particulate Air (HEPA) Filter.. Aerosol Sci. Tech., 19: 94–107. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar] that with a hygroscopic aerosol at humidity below the deliquescent point, or with a non-hygroscopic aerosol, the particulate specific cake resistance decreases as relative humidity increases. For pleated filters as for flat filters, the results reveal that during the formation of the particulate cake, the increase in relative humidity leads to a decrease in the specific cake resistance. When the reduction in filtration area, specific to pleated filters, becomes large, the presence of humidity accelerates the filling of pleats causing a greater pressure drop for a same aerosol mass loading. With a hygroscopic aerosol at a humidity above its deliquescent point, the change in pressure drop through flat or pleated filters is not linear but characteristic of liquid aerosol filtration. The influence of humidity on the efficiency of pleated filters, measured by a soda fluorescein aerosol, has also been studied. For clean filters, the efficiency decreases with increasing relative humidity above 90%. For filters clogged with solid aerosol, change in efficiency versus collected surface mass reaches a maximum whose value depends on the relative humidity; when the aerosol is liquid, the efficiency decreases throughout the clogging.     

Design,synthesis, and preliminary evaluation as antimicrobial activity of novel spiro-1, 3-thiazolidine C-acyclic nucleoside analogs

Synthesis of a new class of 1, 3-thiazolidine nucleoside analogs is described. Reaction of 2-amino-2-deoxy-D-glucopyranose hydrochloride 2 with carbon disulfide yielded 5-hydroxy-4-(D-arabino-1, 2, 3, 4-tetrahydroxybutyl)-thiazolidin-2-thione 3, which on acetylation yielded 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxy-butyl)-thiazolidin-2-thione 4. The acetylated sugar 4 reacted with hydrazonoyl chlorides 1a–f, affording the 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxybutyl)-spiro-1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar]thiazolidine-2,2′ -1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole derivatives 8a–f. The antibacterial activity of the novel 1, 3-thiazolidine-2,2′ -spiro- 1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole nucleoside analogs is highlighted. All compounds with free NH group in the thiazolidine series 8a–f showed significant biological activity against all the standard strains.     

Field Validation of the New Miniature Versatile Aerosol Concentration Enrichment System (mVACES)

Recently a new compact aerosol concentration enrichment system was developed at the University of Southern California, specifically intended to provide particle-laden air at flow rates and pressures suitable for interfacing with on-line continuous aerosol instrumentation for chemical analysis such as mass spectrometers. The re-design and engineering of the miniature Versatile Aerosol Concentration Enrichment System (mVACES) and primarily laboratory-based validation of the individual components and overall system has been previously reported (Geller et al. 2005 Geller, M. D., Biswas, S., Fine, P. M. and Sioutas, C. 2005. A New Compact Aerosol Concentrator for Use in Conjunction with Low Flow-Rate Continuous Aerosol Instrumentation. J. Aerosol Sci., 36: 1006–1022. [CSA][CROSSREF][Crossref], [Web of Science ®] , [Google Scholar]). From September to December 2005, a field performance validation study of the mVACES was conducted in Los Angeles, California at a mixed urban site influenced by both freeway traffic and construction. A variety of continuous and semi-continuous physical and chemical composition measurements were performed to assess the performance of the mVACES compared to accepted methods for validation. Near-ideal performance for aerosol concentration enhancement by the mVACES was observed for mass and number distribution with minimal evidence for distortion of the size distribution. Similarly, near-ideal concentration enhancement factors were observed for both inorganic and organic species suggesting that the mVACES works equally well across the range of externally mixed urban aerosol. The data suggest that aerosol concentration enhancements up to an ideal factor of 20 in a delivered flow on the order of 1.5 liters min^–1 are readily achievable in an urban environment for the ambient conditions studied.     

DYNAMICS OF IMINE AND ACETOPHENONE DERIVATIVES IN SOLUTION STUDIED BY ONE-DIMENSIONAL DIFFUSION-ORDERED NMR SPECTROSCOPY (DOSY)

This paper describes the usefulness of one-dimensional diffusion-ordered NMR spectroscopy (1D-DOSY) in investigating dynamics and interactions of molecules in solution as well as in analyzing the structure of molecules. We synthesized the three imines, N-benzylidene-4-methylbenzene-Sulfonamide (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), N-(4-chloro-benzylidene)4-methyl-benzene-sulfonamide (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and N- (4-methoxybenzylidene)-4-methyl-benzene sulfonamide (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]), and acetophenone (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]) and its three derivatives, 4-chloroacetophenone (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), 4-nitro-acetophenone (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and 4-methoxyaceto -phenone (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). 1D-DOSY was applied to a mixture of compounds (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]) and to a mixture of compounds (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]), (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). Although ¹ H NMR chemical shifts of the molecules in the mixtures resembled one another in the surrounding, we could distinguish signals of the individual molecules in each mixture on the basis of the NMR data and the values of the diffusion coefficient. Also, we could found the correlation of the measured diffusion coefficients and the calculated molecular volumes.     

Characteristics of Aerosol Charge Distribution by Surface-Discharge Microplasma Aerosol Charger (SMAC)

The surface discharge on a dielectric barrier induced by dc pulses was successfully utilized as a stable bipolar ion source for neutralizing submicron aerosol particles where the concentration of positive and negative ions could be adjusted independently (a surface-discharge microplasma aerosol charger: SMAC; Kwon et al., 2005 Kwon, S. B., Sakurai, H., Seto, T. and Kim, Y. J. 2005. Charge Neutralization of Submicron Aerosols Using Surface-Discharge Microplasma. J. Aerosol Sci., in press[CSA] [Google Scholar]). The aim of this study was to determine the charge distribution obtained by the SMAC, which has been qualitatively presented in our previous study, and to investigate the effect of unequal bipolar ion concentration on the charge distribution. For this purpose, we performed quantitative analysis of the charge distribution of monodisperse particles in the size range of 30–200 nm acquired by the SMAC and compared the charge distributions with calculated charge fractions obtained from the diffusion charging theory. The ion parameters were calculated by measuring the ion mobility of positive and negative ions and they were used to obtain the analytic solutions of charge distribution. The charge distributions obtained by the equal or unequal concentration of bipolar ions adjusted by the SMAC showed general agreement with the diffusion charging theory.     

SYNTHESES OF ADDUCTS OF ACTIVE METABOLITES OF CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBONS WITH 2′-DEOXYRIBONUCLEOSIDES

Syntheses are reported for: (1 Harvey, R. G. 1991. Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenicity, Cambridge, , U.K.: Cambridge University Press.  [Google Scholar]) adducts of the quinone metabolites of benzo[a]pyrene (BPQ) and benz[a]anthracene (BAQ) with 2′-deoxyadenosine and 2′-deoxyguanosine; (2 Conney, A. H. 1982. Induction of Microsomal Enzymes by Foreign Chemicals and Carcinogenesis by Polycyclic Aromatic Hydrocarbons. Cancer Res., 42: 4875–4917. [PUBMED][INFOTRIEVE][CSA][PubMed], [Web of Science ®] , [Google Scholar]) ¹⁵ N-labelled analogs of these adducts (four or five nitrogen atoms ¹⁵ N-labelled); (3 Dipple, A. 1994. “Reactions of Polycyclic Aromatic Hydrocarbons with DNA”. In DNA Adducts: Identification and Biological Significance, Edited by: Hemminki, K., Dipple, A., Segerbäck, D., Kadulbar, F. F., Shuker, D. and Bartsch, H. pp. 107–129. IARC Scientific Publication No. 125.  [Google Scholar]) depurinated adducts of BPQ and BAQ with adenine or guanine covalently linked to the N7 or N9 positions of the purine bases; (4 Jeffrey, A. M., Weinstein, I. B., Jennette, K., Grzeskowiak, K., Nakanishi, K., Harvey, R. G., Autrup, H. and Harris, C. 1977. Structures of Benzo[a]pyrene-Nucleic Acid Adducts Formed in Human and Bovine Bronchial Explants. Nature (London)., 269: 348–350. [CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) ¹³ C-labelled derivatives of benzo[a]pyrene, BPQ, benzo[a]pyrene trans-7,8-dihydrodiol, and the benzo[a]pyrene anti-diol epoxide (with ¹³ C-atoms at the 5- and 11-positions); and (5 Jennette, K., Jeffrey, A. M., Blobstein, S. H., Beland, F. A., Harvey, R. G. and Weinstein, I. B. 1977. Characterization of Nucleoside Adducts from the in Vitro Reaction of Benzo[a]pyrene-7,8-dihydrodiol-9,10-oxide or Benzo[a]pyrene-4,5-oxide with Nucleic Acids. Biochemistry, 16: 932–938. [PUBMED][INFOTRIEVE][CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) depurinated adducts formed by reactions of the benzo[a]pyrene radical-cation at the C ⁸ -, N ⁷ -, and N ⁹ -positions of adenine and guanine.     

Numerical Modeling of Nanoparticle Collection Efficiency of Single-Stage Wire-in-Plate Electrostatic Precipitators

The numerical models for predicting the collection efficiency of particles in the size range of 0.3 ～ 10.0 μm in electrostatic precipitators (ESPs) have been well developed. However, for nanoparticles, or particles with the diameter below 100 nm, the existing models can't predict the collection efficiency very well because the electric field and ion concentration distribution were not simulated, or charging models were not adopted appropriately to calculate particle charges. In this study, a 2-D numerical model was developed to predict the nanoparticle collection efficiency in single-stage wire-in-plate ESPs. Laminar flow field was solved by using the Semi-Implicit Method for Pressure-Linked Equation (SIMPLER Method), while electric field strength and ion concentration distribution were solved based on Poisson and diffusion-convection equations, respectively. The charged particle concentration distribution and the particle collection efficiency were then calculated based on the convection-diffusion equation with particle charging calculated by Fuchs diffusion charging theory. The simulated collection efficiencies of 6–100 nm nanoparticles were compared with the experimental data of Huang and Chen (2002 Huang, S. H. and Chen, C. C. 2002. Ultrafine Aerosol Penetration through Electrostatic Precipitators.. Environ. Sci. Technol., 36: 4625–4632. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) for a wire-in-plate dry ESP (aerosol flow rate: 100 L/min, applied voltage: ?15.5 ～ –21.5 kV). Good agreement was obtained. The simulated particle collection efficiencies were further shown to agree with the experimental data obtained in the study for a wire-in-plate wet ESP (Lin et al. 2010 Lin, G. Y., Tsai, C. J., Chen, S. C., Tzu, M. C. and Li, S. N. 2010. An Efficient Single-Stage Wet Electrostatic Precipitator for Fine and Nanosized Particle Control.. Aerosol Sci. Technol, 44: 38–45. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) (aerosol flow rate: 5 L/min, applied voltage: +3.6 ～+4.3 kV) using monodisperse NaCl particles of 10 and 50 nm in diameter. It is expected that the present model can be used to facilitate the design of ESPs for nanoparticle control and electrostatic nanoparticle samplers.     

DNA ADDUCTS OF BENZO[A]PYRENE- AND DIBENZO[A,L]PYRENE-DIOL EPOXIDES IN HUMAN LUNG EPITHELIAL CELLS: KINETICS OF ADDUCT REMOVAL,EFFECTS ON CELL CYCLE CHECKPOINTS,AND GENE EXPRESSION

The fjord-region PAH dibenzo[a,l]pyrene (DBP) is considerably more carcinogenic than the bay-region benzo[a]pyrene (BP). This fact can be ascribed to differences in DNA binding efficiency of their ultimate carcinogenic diol epoxide (DEs) intermediates, differences in structural features of the DNA adducts, and differences in DNA adduct recognition and the subsequent lesion removal by nucleotide excision repair (NER). In order to further substantiate previous findings in cell-free human systems (1 Buterin, T., Hess, M. T., Luneva, N., Geacintov, N. E., Amin, S., Kroth, H., Seidel, A. and Naegeli, H. 2000. Unrepaired Fjord Region Polycyclic Aromatic Hydrocarbon-DNA Adducts in Ras Codon 61 Mutational Hot Spots. Cancer Research, 60: 1849–1856.  [Google Scholar]), cultured cells (2 Luch, A., Kudla, K., Seidel, A., Doehmer, J., Greim, H. and Baird, W. M. 1999. The Level of DNA Modification by (+)-syn-(11S,12R,13S,14R)- and (?)-anti-(11R,12S,13S, 14R)-Dihydrodiol Epoxides of Dibenzo[a,l]pyrene Determined the Effect on the Proteins p53 and p21WAF1 in the Human Mammary Carcinoma Cell Line MCF-7. Carcinogenesis, 20: 859–865.  [Google Scholar]), and in rodents (3 Jankowiak, R., Ariese, F., Hewer, A., Luch, A., Zamzow, D., Hughes, N. C., Phillips, D., Seidel, A., Platt, K. L., Oesch, F. and Small, G. J. 1998. Structure, Conformations, and Repair of DNA Adducts from Dibenzo[a,l]pyrene: 32P-Postlabeling and Fluorescence Studies. Chemical Research in Toxicology, 11: 674–685.  [Google Scholar]) we have studied DNA adduct formation of anti-DE of DBP [(±)-anti-DBPDE], in A549 human epithelial lung carcinoma cells and monitored the levels of adducts as a function of time. A high-performance liquid chromatography (HPLC) procedure that allows monitoring of all cis- and trans-nucleoside adducts of dA and dG was used. Circular dichroism and UV-spectroscopy have been employed to gain information on adduct structural features. Incubation of cells with 0.1 μM (±)-anti-DBPDE resulted in rapid formation of adducts, followed by a decline. After 6 h of incubation about 20% of the adducts remained. Repeating the experiment with 0.01 μM (±)-anti-DBPDE resulted in a correspondingly lower adduct level initially, but in this case a larger proportion (35%) of the adducts remained after 6 h of incubation. Notably, at this time point, similar amounts of adducts are observed with both (±)-anti-DBPDE concentrations studied. Independent of diol epoxide concentration and incubation time, the dA/dG adducts were constant in number (～2.8). However, within the different adduct categories, the adduct distribution seemed to be time dependent. Although the data are preliminary, a selection with regard to adduct removal seems to have taken place. In comparative experiments with (+)-anti-BPDE, no significant difference in rates of adduct removal was evident. Preliminary results from global gene expression analysis, with focus on genes involved in DNA maintenance and cell cycle checkpoints, demonstrate interesting differences in the stress response elicited in the cells following exposure to the distorted and flexible nonplanar DBPDE or the rigid and planar BPDE molecule. As expected some major common induction events were clearly related to the activation of p53-dependent cell cycle checkpoint. However, distinct clusters of gene expression alterations were detected which mark one or other treatment specifically, indicating a high degree of subtlety in the stress response to closely related DNA adduct forming species.     

DETECTION OF KNOWN PHOTOCHEMICAL DECOMPOSITION PRODUCTS OF PAH IN PARTICULATE MATTER FROM POLLUTION EPISODES IN SEOUL,KOREA

Over the past two decades, significant efforts have been expended to identify the photochemical decomposition products of the OH radical reactions of various polycyclic aromatic compounds (PAC), such as naphthalene, methylnaphthalenes, acenaphthene and phenanthrene (1 Lane, D. A. and Tang, H. 1994. Photochemical degradation of polycyclic aromatic compounds. I. Naphthalene.. Polycycl. Aromat. Comp, 5(1): 131–138. [Taylor & Francis Online] , [Google Scholar], 2 Bunce, N. J., Liu, L., Zhu, J. and Lane, D.A. 1997. Reaction of naphthalene and its derivatives with hydroxyl radicals in the gas phase.. Environ. Sci. Technol, 31(8): 2252–2259.  [Google Scholar], 3 Sasaki, J., Aschmann, S.M., Kwok, E.S.C., Atkinson, R. and Arey, J. 1997. Products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene.. Environ. Sci. Technol, 31(11): 3173–3179.  [Google Scholar], 4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 5 Banceu, C. E., Mihele, C.M., Lane, D.A. and Bunce, N.J. 2001. Reactions of methylated naphthalenes with hydroxyl radicals under simulated atmospheric conditions.. Polycycl. Aromat. Comp, 18(4): 415–426. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 6 Wang, L., Atkinson, R. and Arey, J. 2007. Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C1- and C2-alkylnaphthalenes.. Environ. Sci. Technol, 41(8): 2803–2810.  [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar]). Although these parent PAC are predominantly found in the gas phase, many of their oxidation products have been found largely in the particle phase (4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar], 8 Mihele, C. M., Wiebe, H.A. and Lane, D.A. 2002. Particle formation and gas/particle partition measurements of the products of the naphthalene-OH radical reaction in a smog chamber. Polycycl. Aromat. Comp., 22: 729–736. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). These products include diones, hydroxy-, and nitrated products as well as many products resulting from ring-opening steps. It is, or should be, the goal of every laboratory study on atmospheric processes to apply the laboratory results to real world samples. To this end, we have obtained particulate matter air samples, as well as some smog episode samples, from Seoul Korea and have searched for the known decomposition products of the above mentioned PAC. To eliminate the use of chlorinated solvents used in the extraction and analysis of particulate matter samples, we have been utilizing the direct thermal desorption of small (4 mm diameter) punches of filters followed by Multidimensional Gas Chromatography-Time of Flight Mass Spectrometry (TD-GCxGC-TOFMS) for the analysis of the desorbed compounds. So far, we have detected 14 of the known decomposition products of naphthalene, acenaphthene and phenanthrene in the Seoul pollution episode samples. These include: 1-hydroxynaphthalene, (E) 2-formylcinnamaldehyde, phthalic anhydride, phthalide, 1,2-naphthalic anhydride, 9-hydroxyphenanthrene and dibenzopyrone.     

PENTACYCLIC TRITERPENE CONSTITUENTS OF YELLOW BIRCH BARK FROM QUEBEC*

ABSTRACT

Birch bark represents an abundant, and currently under-utilized, natural resource. Yellow birch (Betula alleghaniensis), the emblem tree of Quebec, is commercially important and one of the most widespread birch species in the province, but the use of its bark is limited. It is only used as a low value fuel source in solid wood products industries. Yellow birch bark triterpene constituents such as lupeol, betulin and betulinic acid have been described to have high biological activity. The yellow birch bark triterpene constituents such as betulin and certain derivatives of this natural substance have demonstrated interesting therapeutic properties. For example, betulinic acid has been shown to possess anti-tumor activity against human melanoma cells both in vitro and in vivo models. Its mechanism of action consists in the induction of apoptosis or cellular suicide in the cancer cells without affecting healthy cells.[14] Pisha, E., Chai, H., Lee, I.-S., Chagwedera, T.E., Farnsworth, N.R., Cordell, G.A., Beecher, C.W.W., Fong, H.H.S., Kinghorn, A.D., Brown, M., Wani, M.C., Wall, M.E., Hieken, T.J., Das Gupta, T.K. and Pezzuto, J.M. 1995. Nature Medicine, 1: 1046[Crossref], [PubMed], [Web of Science ®] , [Google Scholar] These natural products confer added value to this tree. In this study, we investigated the triterpenoid composition of the outer bark of B. alleghaniensis from three locations in Quebec: Saint-Damien de Bellechasse, Saint-Félix-d’Otis, and Duchesnay. Eight triterpenes not previously reported in the bark of yellow birch were detected in this research. The betulonic aldehyde was identified as a new yellow birch bark constituent in bark samples from all sites, while the betulinic aldehyde and the oleanane type triterpenes were only detected in the sample from Saint-Félix-d’Otis. To our knowledge, this is the first time that the oleanane-type triterpenes are identified in yellow birch bark.

     

Ion Beam Charging of Aerosol Nanoparticles

In our ongoing efforts to achieve the high-efficiency charging of aerosol nanoparticles under low-pressure conditions, our group has recently developed an ion beam aerosol charger (IBAC) that ionizes aerosol nanoparticles using an He⁺ ion beam (Seto et al. 2003 Seto, T., Orii, T., Hirasawa, M., Aya, N. and Shimura, H. 2003. Ion Beam Charging of Silicon Nanoparticles in Helium Background Gas—Design of the Ion Beam Aerosol Charger (IBAC). Rev. Sci. Inst., 74: 3027–3030. [CROSSREF][Crossref] , [Google Scholar]). In earlier studies we have observed both increases and decreases in the currents from the charged particles, depending on the pressure when the polydisperse particles were irradiated by the ion beam. None of our previous studies elucidated the mechanisms of the charging itself, however. In the present paper we evaluate the charging probability of monodisperse aerosol nanoparticles using a low-pressure differential mobility analyzer (LP-DMA) and aerosol electrical condenser (AEC). The particles were negatively charged by the attachment of free electrons generated via the ionization of carrier gas by ion beam irradiation under a pressure of more than 350 Pa. A charging probability of more than 60% was obtained experimentally for the particles of 10–40 nm in mobility diameter under the pressure of 350–650 Pa. The mobility of the particles was almost the same before and after charging in a tandem LP-DMA analysis, with no multiply charged particles observed. The charging probability of nanoparticles was estimated based on the diffusion charging theory. Lastly, experiments were performed to demonstrate the performance of the IBAC in the charging of neutral particles in comparison with that of an α-ray source.     

Methodology for Performance Evaluation of Dust Control Systems with an Application to Electrostatic Precipitators

A general methodology is presented that enables rigorous estimation of the total collection efficiency and the size distribution of particles penetrating dust control systems. This methodology assumes lognormal inlet particle-size distributions and can be used with fractional efficiency formulations that predict, under such conditions, lognormal outlet particle-size distributions. Multimodal inlet particle distributions can be accommodated additively. This methodology is applied to Electrostatic Precipitator Systems (ESPs), with the Nobrega et al. (2004) Nobrega, S. W., Falaguasta, M. C. R. and Coury, J. R. 2004. A Study of a Wire-Plate Electrostatic Precipitator Operating in the Removal of Polydispersed Particles. Braz. J. Chem. Eng., 21(2): 275–284. [Crossref], [Web of Science ®] , [Google Scholar] model selected for predicting their fractional efficiencies. For ease of use, a graphical solution has been developed for the Nobrega et al. fractional efficiency relations, but its availability is not a prerequisite for the application of the general methodology. For the latter, the fractional efficiencies corresponding to three particle diameters need to be estimated and this can be done either graphically or numerically using the model of Nobrega et al. or any other fractional efficiency formulation of interest.

Fine particles emerge as the most important pollutant worldwide in terms of human health, creating thus the need for credible particle size-specific inventories. In line with the above, a generic and rigorous method, capable of producing size-specific emission estimates from uncontrolled and controlled sources, has been developed (Economopoulou and Economopoulos 2001 Economopoulou, A. A. and Economopoulos, A. P. 2001. Method for Estimating Size-Specific Particulate Emission Inventories. J. Environ. Eng., ASCE, 127: 1139–1148. [Crossref], [Web of Science ®] , [Google Scholar]). For controlled sources, this method relies on the development of easy to use models that predict the total efficiency and the lognormal size distribution of particles penetrating the control systems used. Such models have already been developed for dry cyclone separators (Economopoulou and Economopoulos 2002a Economopoulou, A. A. and Economopoulos, A. P. 2002a. Rapid Performance Evaluation and Optimal Sizing of Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 275–285. [Crossref], [Web of Science ®] , [Google Scholar], 2002b Economopoulou, A. A. and Economopoulos, A. P. 2002b. Size Distribution of Particles Penetrating Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 919–928. [Crossref], [Web of Science ®] , [Google Scholar]) and venturi scrubbers (Economopoulou and Harrison 2007a Economopoulou, A. A. and Harrison, R. M. 2007a. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part I: Rapid Collection Efficiency Evaluation. Aerosol Sci. Technol., 41: 51–62. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 2007b Economopoulou, A. A. and Harrison, R. M. 2007b. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part II: Size Distribution of Penetrating Particles. Aerosol Sci. Technol., 41: 63–74. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). The present methodology extends the use of the inventory methodology to ESP-controlled sources and, in addition, it provides a generalized basis for covering other types of control systems with any fractional efficiency formulation considered appropriate.