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1.
Glob Health Action ; 17(1): 2370100, 2024 Dec 31.
Article in English | MEDLINE | ID: mdl-38940815

ABSTRACT

BACKGROUND: Although there is increasing awareness of the health risks of air pollution as a global issue, few studies have focused on the methods for assessing individuals' perceptions of these risks. This scoping review aimed to identify previous research evaluating individuals' perceptions of air pollution and its health effects, and to explore the measurement of perceptions, as a key resource for health behaviour. METHODS: The review followed the methodological framework proposed by Arksey and O'Malley. PubMed and Web of Science were searched. After initial and full-text screening, we further selected studies with standardised scales that had previously been tested for reliability and validity in assessing awareness and perceptions. RESULTS: After full-text screening, 95 studies were identified. 'Perception/awareness of air quality' was often measured, as well as 'Perception of health risk.' Only nine studies (9.5%) used validated scaled questionnaires. There was considerable variation in the scales used to measure the multiple dimensions of risk perception for air pollution. CONCLUSION: Few studies used structured scales to quantify individuals' perceptions, limiting comparisons among studies. Standardised methods for measuring health risk perception are needed.


Main findings: Among 95 studies assessing health risk perception of air pollution, only nine studies used standardised scales.Added knowledge: There was considerable variation in the scales measuring the multiple dimensions of risk perception for air pollution, which makes comparison among the studies difficult.Global health impact for policy and action: This review highlights the need for the development of globally standardised scale to measure the health risk perception of air pollution.


Subject(s)
Air Pollution , Humans , Air Pollution/adverse effects , Air Pollution/analysis , Health Knowledge, Attitudes, Practice , Risk Assessment/methods , Perception , Surveys and Questionnaires
2.
Sci Rep ; 13(1): 13201, 2023 Aug 14.
Article in English | MEDLINE | ID: mdl-37580480

ABSTRACT

Exposure to particulate matter less than 2.5 µm in diameter (PM2.5) is a cause of concern in cities and major emission regions of northern India. An intensive field campaign involving the states of Punjab, Haryana and Delhi national capital region (NCR) was conducted in 2022 using 29 Compact and Useful PM2.5 Instrument with Gas sensors (CUPI-Gs). Continuous observations show that the PM2.5 in the region increased gradually from < 60 µg m-3 in 6-10 October to up to 500 µg m-3 on 5-9 November, which subsequently decreased to about 100 µg m-3 in 20-30 November. Two distinct plumes of PM2.5 over 500 µg m-3 are tracked from crop residue burning in Punjab to Delhi NCR on 2-3 November and 10-11 November with delays of 1 and 3 days, respectively. Experimental campaign demonstrates the advantages of source region observations to link agricultural waste burning and air pollution at local to regional scales.

3.
J Environ Manage ; 311: 114784, 2022 Mar 10.
Article in English | MEDLINE | ID: mdl-35279490

ABSTRACT

Low-cost PM2.5 sensors are now used worldwide to assess air pollution. However, their operation is generally challenging in severely cold regions like Siberia, Alaska, the Arctic, and Antarctica. We made an insulation box with automatic internal temperature control developed for a low-cost PM2.5 sensor to maintain a warm operational environment with four light-bulb heaters when the air temperature inside of the insulation box falls slightly below 5 °C under the current preset temperature setting. We confirmed the performance of the temperature controller with four light-bulb heaters in a -25 °C cold temperature room. In addition, we found that the insulation box must be attached to a small electric fan to forcibly ventilate the box to accurately reflect the external ambient air conditions into the insulating box. Our observations with the data from our low-cost PM2.5 sensor fitted with the insulation box were validated against the Sapporo National Ambient Air Monitoring Station (NAAMS) data in Sapporo, Japan, showing good correspondence with the hourly station-measured data. Then, we installed our PM2.5 measurement system on the roof of the International Arctic Research Center (IARC), University of Alaska Fairbanks, Alaska, USA, in June 2019. The sensor sufficiently captured two instances of significant increases in PM2.5 mass concentrations during the Alaskan wildfires in the summer of 2019. Our developed insulation box for low-cost PM2.5 sensors, called "the portable PM2.5 measurement system for cold regions", will help assess air quality in many cold regions in future studies.

4.
Sci Rep ; 10(1): 13442, 2020 08 10.
Article in English | MEDLINE | ID: mdl-32778673

ABSTRACT

Delhi, a tropical Indian megacity, experiences one of the most severe air pollution in the world, linked with diverse anthropogenic and biomass burning emissions. First phase of COVID-19 lockdown in India, implemented during 25 March to 14 April 2020 resulted in a dramatic near-zeroing of various activities (e.g. traffic, industries, constructions), except the "essential services". Here, we analysed variations in the fine particulate matter (PM2.5) over the Delhi-National Capital Region. Measurements revealed large reductions (by 40-70%) in PM2.5 during the first week of lockdown (25-31 March 2020) as compared to the pre-lockdown conditions. However, O3 pollution remained high during the lockdown due to non-linear chemistry and dynamics under low aerosol loading. Notably, events of enhanced PM2.5 levels (300-400 µg m-3) were observed during night and early morning hours in the first week of April after air temperatures fell close to the dew-point (~ 15-17 °C). A haze formation mechanism is suggested through uplifting of fine particles, which is reinforced by condensation of moisture following the sunrise. The study highlights a highly complex interplay between the baseline pollution and meteorology leading to counter intuitive enhancements in pollution, besides an overall improvement in air quality during the COVID-19 lockdown in this part of the world.


Subject(s)
Air Pollutants/analysis , Betacoronavirus , Coronavirus Infections/epidemiology , Coronavirus Infections/prevention & control , Pandemics/prevention & control , Particulate Matter/analysis , Pneumonia, Viral/epidemiology , Pneumonia, Viral/prevention & control , Quarantine/methods , Weather , Aerosols/analysis , Air Pollution/analysis , COVID-19 , Cities/epidemiology , Coronavirus Infections/virology , Environmental Monitoring/methods , Humans , India/epidemiology , Ozone/analysis , Pneumonia, Viral/virology , SARS-CoV-2 , Temperature
5.
Article in English | MEDLINE | ID: mdl-32326387

ABSTRACT

In the present study, we measured fine particulate matter (PM2.5) on the daily route of our study participant in order to determine her exposure and dose of PM2.5 in every microenvironment (ME). The measuring instrument, created by Nagoya University and Panasonic Corporation, Japan, was carried close to the breathing zone most of the time. Each data point was collected for 10-30 s or 2-6 cycles/min for 24 h from 1 October 2018 to 30 December 2018. Public transportation showed the highest level of PM2.5 compared with other MEs, including residence apartments, houses (ger district), the National University of Mongolia (NUM), food courts or restaurants, and other indoor locations. The personal daily average exposure to PM2.5 was 35 µg/m3 on 4 November 2018; on the other hand, this value was evaluated as the highest level of exposure compared to other measurement days. Interestingly, the study participant's exposure and dose of PM2.5 was lower than those stated in the World Health Organization (WHO) air quality guidelines, with 25 µg/m3 from 4:00 to 7:00.


Subject(s)
Air Pollutants/analysis , Air Pollution/analysis , Environmental Exposure/analysis , Environmental Monitoring/methods , Particulate Matter/analysis , Cities , Female , Housing , Humans , Japan , Restaurants , Transportation
6.
Ecotoxicol Environ Saf ; 194: 110432, 2020 May.
Article in English | MEDLINE | ID: mdl-32169727

ABSTRACT

It is important to have good indoor air quality, especially in indoor office environments, in order to enhance productivity and maintain good work performance. This study investigated the effects of indoor office activities on particulate matter of less than 2.5 µm (PM2.5) and ozone (O3) concentrations, assessing their potential impact on human health. Measurements of indoor PM2.5 and O3 concentrations were taken every 24 h during the working days in five office environments located in a semi-urban area. As a comparison, the outdoor concentrations were derived from the nearest Continuous Air Quality Monitoring Station. The results showed that the average 24 h of indoor and outdoor PM2.5 concentrations were 3.24 ± 0.82 µg m-3 and 17.4 ± 3.58 µg m-3 respectively, while for O3 they were 4.75 ± 4.52 ppb and 21.5 ± 5.22 ppb respectively. During working hours, the range of PM2.5 concentrations were 1.00 µg m-3 to 6.10 µg m-3 while for O3 they were 0.10 ppb to 38.0 ppb. The indoor to outdoor ratio (I/O) for PM2.5 and O3 was <1, thus indicating a low infiltration of outdoor sources. The value of the hazard quotient (HQ) for all sampling buildings was <1 for both chronic and acute exposures, indicating that the non-carcinogenic risks are negligible. Higher total cancer risk (CR) value for outdoors (2.67E-03) was observed compared to indoors (4.95E-04) under chronic exposure while the CR value for acute exposure exceeded 1.0E-04, thus suggesting a carcinogenic PM2.5 risk for both the indoor and outdoor environments. The results of this study suggest that office activities, such as printing and photocopying, affect indoor O3 concentrations while PM2.5 concentrations are impacted by indoor-related contributions.


Subject(s)
Air Pollutants, Occupational/analysis , Air Pollution, Indoor/analysis , Environmental Monitoring/methods , Ozone/analysis , Particulate Matter/analysis , Humans , Malaysia , Particle Size , Risk Assessment
7.
Ecotoxicol Environ Saf ; 170: 739-749, 2019 Apr 15.
Article in English | MEDLINE | ID: mdl-30583285

ABSTRACT

It is important to assess indoor air quality in school classrooms where the air quality may significantly influence school children's health and performance. This study aims to determine the concentrations of PM2.5 and dust chemical compositions in indoor and outdoor school classroom located in Kuala Lumpur City Centre. The PM2.5 concentration was measured from 19th September 2017-16th February 2018 using an optical PM2.5 sensor. Indoor and outdoor dust was also collected from the school classrooms and ion and trace metal concentrations were analysed using ion chromatography (IC) and inductively couple plasma-mass spectrometry (ICP-MS) respectively. This study showed that the average indoor and outdoor 24 h PM2.5 was 11.2 ±â€¯0.45 µg m-3 and 11.4 ±â€¯0.44 µg m-3 respectively. The 8 h PM2.5 concentration ranged between 3.2 and 28 µg m-3 for indoor and 3.2 and 19 µg m-3 for outdoor classrooms. The highest ion concentration in indoor dust was Ca2+ with an average concentration of 38.5 ±â€¯35.0 µg g-1 while for outdoor dust SO42- recorded the highest ion concentration with an average concentration of 30.6 ±â€¯9.37 µg g-1. Dominant trace metals in both indoor and outdoor dust were Al, Fe and Zn. Principle component analysis-multiple linear regression (PCA-MLR) demonstrated that the major source of indoor dust was road dust (69%), while soil dominated the outdoor dust (74%). Health risk assessment showed that the hazard quotient (HQ) value for non-carcinogenic trace metals was < 1 while the total cancer risk (CR) value for carcinogenic elements was below the acceptable limit for both indoor and outdoor dust through dermal and inhalation pathways, but not the ingestion pathway. This study suggests indoor contributions of PM2.5 concentrations are due to the activities of the school children while the compositions of indoor and outdoor dust are greatly influenced by the soil/earth source plus industrial and traffic contribution.


Subject(s)
Air Pollutants/analysis , Air Pollution, Indoor/analysis , Dust/analysis , Environmental Exposure/analysis , Schools , Calcium/analysis , Child , Environmental Monitoring , Humans , Ions/analysis , Malaysia , Particle Size , Risk Assessment , Sulfates/analysis , Trace Elements/analysis
8.
Environ Sci Technol ; 52(5): 2566-2574, 2018 03 06.
Article in English | MEDLINE | ID: mdl-29385329

ABSTRACT

Oxidation of isoprene by hydroxyl radical (OH), ozone (O3), or nitrate radical (NO3) leads to the formation of secondary organic aerosol (SOA) in the atmosphere. This SOA contributes to the radiation balance by scattering and absorbing solar radiation. In this study, the effect of oxidation processes on the wavelength-dependent complex refractive index (RI) of SOA generated from isoprene was examined. Oxidation conditions did not have a large effect on magnitude and wavelength dependence of the real part of the RI. In the case of SOA generated in the presence of sulfur dioxide (SO2), significant light absorption at short visible and ultraviolet wavelengths with the imaginary part of the RI, up to 0.011 at 375 nm, was observed during oxidation with OH. However, smaller and negligible values were observed during oxidation with O3 and NO3, respectively. Moreover, in the absence of SO2, light absorption was not observed regardless of the oxidation process. There was an empirical correlation between the imaginary part of the RI and the average degree of unsaturation of organic molecules. The results obtained herein demonstrate that oxidation processes should be considered for estimating the radiative effect of isoprene-derived SOA.


Subject(s)
Hemiterpenes , Refractometry , Aerosols , Butadienes , Oxidation-Reduction , Pentanes
9.
Isotopes Environ Health Stud ; 53(6): 646-659, 2017 Dec.
Article in English | MEDLINE | ID: mdl-28756690

ABSTRACT

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO2 and water vapour were observed. The isotope ratios of both CO2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ13C-CO2 and δ18O-CO2 increased, while δ2H-H2Ov and δ18O-H2Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO2 and H2Ov could be used as a tracer of meteorological information.


Subject(s)
Atmosphere/chemistry , Carbon Dioxide/analysis , Carbon Isotopes/analysis , Cities , Deuterium/analysis , Oxygen Isotopes/analysis , Steam/analysis , Cyclonic Storms , Japan , Lasers , Meteorology , Spectrum Analysis
10.
Isotopes Environ Health Stud ; 52(6): 603-18, 2016 Dec.
Article in English | MEDLINE | ID: mdl-27142631

ABSTRACT

We conducted continuous, high time-resolution measurements of CO2 and water vapour isotopologues ((16)O(12)C(16)O, (16)O(13)C(16)O and (18)O(12)C(16)O for CO2, and H2(18)O for water vapour) in a red pine forest at the foot of Mt. Fuji for 9 days from the end of July 2010 using in situ absorption laser spectroscopy. The δ(18)O values in water vapour were estimated using the δ(2)H-δ(18)O relationship. At a scale of several days, the temporal variations in δ(18)O-CO2 and δ(18)O-H2O are similar. The orders of the daily Keeling plots are almost identical. A possible reason for the similar behaviour of δ(18)O-CO2 and δ(18)O-H2O is considered to be that the air masses with different water vapour isotopic ratios moved into the forest, and changed the atmosphere of the forest. A significant correlation was observed between δ(18)O-CO2 and δ(13)C-CO2 values at nighttime (r(2)≈0.9) due to mixing between soil (and/or leaf) respiration and tropospheric CO2. The ratios of the discrimination coefficients (Δa/Δ) for oxygen (Δa) and carbon (Δ) isotopes during photosynthesis were estimated in the range of 0.7-1.2 from the daytime correlations between δ(18)O-CO2 and δ(13)C-CO2 values.


Subject(s)
Carbon Dioxide/analysis , Forests , Isotopes/analysis , Spectrum Analysis/methods , Steam , Lasers
11.
Appl Opt ; 49(19): 3762-7, 2010 Jul 01.
Article in English | MEDLINE | ID: mdl-20648143

ABSTRACT

We report on the development of a low-cost and compact instrument for quantifying atmospheric NO(2) concentrations by detecting NO(2) fluorescence using a commercial light-emitting diode around 435 nm as a fluorescence excitation light source. The minimum detectable limit of the NO(2) instrument developed has been estimated to be 9.8 parts per billion of volume mixing ratio (ppbv) in a 60 s integration time and with a signal-to-noise ratio of 2.

12.
Anal Sci ; 23(5): 507-12, 2007 May.
Article in English | MEDLINE | ID: mdl-17495392

ABSTRACT

A real-time analysis of secondary organic aerosol (SOA) particles formed from cyclohexene ozonolysis in a smog chamber was performed using a laser-ionization single-particle aerosol mass spectrometer (LISPA-MS). The instrument obtains both size and chemical compositions of individual aerosol particles with a high time-resolution (approximately 2 s at the maximum). Both positive and negative-ion mass spectra are obtained. Standard particles generated from dicarboxylic acid solutions using an atomizer were also analyzed. For both standard and SOA particles, the negative-ion mass spectra provided information about the molecular weights of the organic compounds in the particles, since the intense ions in the negative-ion mass spectra are mainly attributable to the molecular-related ions [M-H]-. It was demonstrated that the real-time single-particle analysis of SOA particles by the LISPA-MS technique can reveal the formation and transformation processes of SOA particle in smog chambers.

13.
J Phys Chem A ; 111(7): 1271-6, 2007 Feb 22.
Article in English | MEDLINE | ID: mdl-17266289

ABSTRACT

The gas-phase reactions of Cl atoms with acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, and cyclopentanone at 295 +/- 2 K were studied using pulsed laser photolysis vacuum UV laser-induced fluorescence (PLP-LIF) techniques. Cl(2P(3/2)) atoms were produced by photolysis of Cl2 at 351 nm and monitored by LIF spectroscopy at 134.72 nm (3p(5) 2P(3/2)-3p(4)4s 2P(3/2) transition). Rate coefficients for reactions of Cl atoms with acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, and cyclopentanone are (2.30 +/- 0.12) x 10(-12), (4.08 +/- 0.21) x 10(-11), (1.23 +/- 0.13) x 10(-10), (8.87 +/- 0.92) x 10(-11), (2.08 +/- 0.32) x 10(-10), (1.43 +/- 0.19) x 10(-10) and (1.16 +/- 0.12) x 10(-10) cm3 molecule(-1) s(-1), respectively. The results for acetone and butanone are consistent with previous studies. The results for 2-pentanone, 3-pentanone, 2-hexanone, and 3-hexanone are approximately a factor of 2-3 higher than those from previous absolute rate studies. Likely explanations for these discrepancies are discussed. Tropospheric lifetimes of ketones with respect to reaction with Cl atoms are estimated and discussed.

14.
Appl Opt ; 46(6): 907-15, 2007 Feb 20.
Article in English | MEDLINE | ID: mdl-17279136

ABSTRACT

We report on the development of a highly sensitive detection system for measuring atmospheric NO(2) by means of a laser-induced fluorescence (LIF) technique at 473 nm using a diode-pumped Nd:YAG laser. A GaN-based laser diode emitting at 410 nm is also used as an alternative fluorescence-excitation source. For laboratory calibrations, standard NO(2) gas is diluted with synthetic air and is introduced into a fluorescence-detection cell. The NO(2) LIF signal is detected by a photomultiplier tube and processed by a photon-counting method. The minimum detectable limits of the NO(2) instrument developed have been estimated to be 0.14 ppbv and 0.39 ppbv (parts per billion, 10(-9), by volume) in 60 s integration time (signal-to-noise ratio of 2) for 473 and 410 nm excitation systems, respectively. Practical performance of the instrument has been demonstrated by the 24 hour continuous measurements of ambient NO(2) in a suburban area.

15.
J Phys Chem A ; 109(48): 10897-902, 2005 Dec 08.
Article in English | MEDLINE | ID: mdl-16331933

ABSTRACT

Formation of the ground-state nitrogen atom, N((4)S), following 193.3-nm ArF laser irradiation of NO and NO(2) was detected directly by a technique of laser-induced fluorescence (LIF) spectroscopy at 120.07 nm. Tunable vacuum ultraviolet (VUV) laser radiation around 120.07 nm was generated by two-photon resonance four-wave sum frequency mixing in Hg vapor. Photoexcitation processes of NO and NO(2) giving rise to the N((4)S) formation are discussed on the basis of the Doppler profiles of the nascent N((4)S) atoms produced from the photolysis of NO and NO(2) and the photolysis laser-power dependence of the N((4)S) signal intensities. Using laser flash photolysis and vacuum ultraviolet laser-induced fluorescence detection, the kinetics of the reactions of N((4)S) with NO and NO(2) have been investigated at 295 +/- 2 K. The rate constants for the reactions of N((4)S) with NO and NO(2) were determined to be (3.8 +/- 0.2) x 10(-11) and (7.3 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), respectively, where the quoted uncertainties are 2sigma statistical uncertainty including estimated systematic error.

16.
J Phys Chem A ; 109(40): 9061-9, 2005 Oct 13.
Article in English | MEDLINE | ID: mdl-16332012

ABSTRACT

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm3 molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield >75% and CH2CHF2 radicals in a yield <25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(2P(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm3 molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl(2P(1/2)) (denoted Cl) in collisions with CH3CHF2 was determined to be k(Cl + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm3 molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NO(x). In the absence of NO(x)(), the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NO(x), the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NO(x)] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O2 to give CH3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate >10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (>50 mTorr), NO(x) is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.

17.
J Phys Chem A ; 109(11): 2552-8, 2005 Mar 24.
Article in English | MEDLINE | ID: mdl-16833558

ABSTRACT

Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is a ubiquitous pollutant that is primarily destroyed by either thermal or photochemical mechanisms. We have investigated the photochemical destruction of PAN using a combination of laser pulsed photolysis and cavity ring-down spectroscopic detection of the NO3 photoproduct. We find that the nitrate radical quantum yield from the 289 nm photolysis of PAN is Phi(NO3)PAN = 0.31 +/- 0.08 (+/-2 sigma). The quantum yield is determined relative to that of dinitrogen pentoxide, which is assumed to be unity, under identical experimental conditions. The instrument design and experimental procedure are discussed as well as auxiliary experiments performed to further characterize the performance of the optical cavity and photolysis system.

18.
J Phys Chem A ; 109(12): 2855-60, 2005 Mar 31.
Article in English | MEDLINE | ID: mdl-16833601

ABSTRACT

Cl(2P(3/2)) and Cl*(2P(1/2)) atoms produced from the photodissociation of chlorofluorocarbons (CFCs) and chlorinated hydrocarbons at 193.3 nm have been detected quantitatively by a technique of vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy at 135.2 and 134.7 nm for j = 1/2 and 3/2, respectively. The quantum yields for total Cl-atom formation in the 193.3 nm photolysis at 295 +/- 2 K have been determined to be 1.03 +/- 0.09, 1.01 +/- 0.08, 1.03 +/- 0.08, 1.03 +/- 0.10, 1.41 +/- 0.14, 1.02 +/- 0.08, and 0.98 +/- 0.08 for CF2Cl2, CFCl3, CH2Cl2, CHCl3, CCl4, CHFCl2, and CCl3CF3, respectively. Those results suggest that the single C-Cl bond rupture always occurs in the photolysis of these molecules except for CCl4. Formation of two Cl atoms partly takes place in the photodissociation of CCl4. The quantum yields for total Cl-atom formation in the 193.3 nm photolysis of CHBr2Cl and CHBrClCF3 are 0.27 +/- 0.02 and 0.28 +/- 0.02, respectively, which suggests that the C-Br bond rupture is a main channel in the photodissociation processes. The branching ratios between the spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), have also been determined for the photodissociation of the chlorinated compounds at 193.3 nm. The UV photodissociation processes giving rise to formation of Cl(2P(j)) atoms from the chlorinated compounds studied here have been discussed.

19.
J Phys Chem A ; 109(17): 3935-40, 2005 May 05.
Article in English | MEDLINE | ID: mdl-16833712

ABSTRACT

The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm3 molecule(-1) s(-1)): k(Cl(2P(3/2))+CH3OH) = (5.35 +/- 0.24) x 10(-11), k(Cl(2P(3/2))+C2H5OH) = (9.50 +/- 0.85) x 10(-11), k(Cl(2P(3/2))+n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(2P(3/2))+i-C3H7OH) = (9.11 +/- 0.60) x 10(-11). Measured rate constants for total removal of Cl*(2P(1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-10), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(2P(1/2)) atoms have 2.52 kcal/mol more energy than Cl(2P(3/2)), the rates of chemical reaction of Cl*(2P(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(2P(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.

20.
Chem Rev ; 103(12): 4767-82, 2003 Dec.
Article in English | MEDLINE | ID: mdl-14664632
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