Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 2. Partitioning of polychlorinated dibenzodioxins,polychlorinated dibenzofurans,and polycyclic aromatic hydrocarbons to quartz fiber filters

Gas/particle distributions of atmospheric semi-volatile organic compounds (SOCs) are often measured using filter/sorbent samplers. Unfortunately, the adsorption of gaseous SOCs onto a filter can cause positive biases in the measured particle-phase concentrations, and negative biases in the measured gas-phase concentrations. When quartz fiber filters (QFFs) are used, surface-area-normalized gas/quartz partition coefficient (K_p,s, m³ m⁻²) values will be useful when estimating the magnitudes of these errors. Gas/QFF K_p,s values have been reported in the literature only for polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. Gas/QFF K_p,s values were measured here for a series of polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and also for a range of PAHs. Within each of the three individual compound classes, plots of log K_p,s vs. log p_L^o (sub-cooled liquid vapor pressure) were found to be linear with slopes of approximately −1. At relative humidity (RH)=25%, the pooled log K_p,s data at 25°C for the three compound classes were correlated with log p_L^o nearly as well (r²=0.95) as were the data for the individual compound classes (r²≈0.97). In general, the K_p,s values for the PAHs and PCDD/PCDFs studied were found to be about a factor of 2 larger for partitioning to clean QFFs at RH=25% than for TMFs at RH=21–52%. Backup QFFs used in filter/sorbent sampling in a suburban area yielded K_p,s values for PAHs at RH=37% that were significantly lower than for clean QFFs at the same RH. (This may have been the result of the adsorption of ambient organic compounds that at least partially blocked the direct adsorption of the SOCs to the QFF surface). Therefore, when QFFs are used to separate atmospheric gas- and particle-phase SOCs, corrections for compound-dependent gas adsorption artifacts for QFFs may need to be carried out using K_p,s values that were obtained with ambient backup QFFs.     

A review of current knowledge concerning dry deposition of atmospheric mercury

The status of the current knowledge concerning the dry deposition of atmospheric mercury, including elemental gaseous mercury (Hg⁰), reactive gaseous mercury (RGM), and particulate mercury (Hg_p), is reviewed. The air–surface exchange of Hg⁰ is commonly bi-directional, with daytime emission and nighttime deposition over non-vegetated surfaces and vegetated surfaces with small leaf area indices under low ambient Hg⁰ conditions. However, daytime deposition has also been observed, especially when the ambient Hg⁰ is high. Typical dry deposition velocities (V_d) for Hg⁰ are in the range of 0.1–0.4 cm s^?1 over vegetated surfaces and wetlands, but substantially smaller over non-vegetated surfaces and soils below canopies. Meteorological, biological, and soil conditions, as well as the ambient Hg⁰ concentrations all play important roles in the diurnal and seasonal variations of Hg⁰ air–surface exchange processes. Measurements of RGM deposition are limited and are known to have large uncertainties. Nevertheless, all of the measurements suggest that RGM can deposit very quickly onto any type of surface, with its V_d ranging from 0.5 to 6 cm s^?1. The very limited data for Hg_p suggest that its V_d values are in the range of 0.02–2 cm s^?1.A resistance approach is commonly used in mercury transport models to estimate V_d for RGM and Hg_p; however, there is a wide range of complexities in the dry deposition scheme of Hg⁰. Although resistance-approach based dry deposition schemes seem to be able to produce the typical V_d values for RGM and Hg⁰ over different surface types, more sophisticated air–surface exchange models have been developed to handle the bi-directional exchange processes. Both existing and newly developed dry deposition schemes need further evaluation using field measurements and intercomparisons within different modelling frameworks.     

Cooling Pond Steam Fog

This paper is responsive to needs to describe and predict the environmental effects from power plant cooling ponds. A study was made to determine atmospheric and pond surface conditions required for steam fog to occur from power plant cooling ponds, to define the dimensions of the fog, and to collect data on deposition of ice. Data, collected principally at the 4-Corners Plant over a three-year period, included water surface temperature, ambient meteorological conditions and occurrence and magnitude of steam fog and ice deposition. With strong winds, the fog extended onshore without lifting. With light winds, the fog extended some distance onshore but then lifted to form stratus. With almost calm winds, the steam fog lifted over the pond and drifted downwind as stratus. Steam fog was observed in winds to 28 mph, air-water temperature differences from 21.5° to 68°F and in atmospheric stability categories C, D, E, and F. A fog index number, Ar/(e_s — e_a)°F/mbs, was defined and used for data interpretation, where Ar is temperature of water less temperature of ambient air, e_s is the saturation vapor pressure of the ambient air and e_a is the actual vapor pressure of the ambient air. The probability of occurrence of steam fog as a function of the fog index number varied from 0.04 for an index number less than 10 to 1.00 for an index number greater than 90. From the data, if fog occurred, its extent along the ground was &#x2265;100 feet 88% of the time, &#x2265;500 feet 35% of the time, &#x2265;1000 feet 18% of the time, and &#x2265;5000 feet 12% of the time. If stratus occurred its extent above ground was &#x2265;1 mile 91% of the time, &#x2265;5 miles 55% of the time and &#x2265;10 miles 36% of the time. Measurements showed that steam fog droplet sizes predominate in the 10 micron diameter size. Values of liquid water content up to 0.20 g/m³ were reported. Ice accretion data show build-up rates from 0.23 to 13 mm/hr of rime.     

Comparison of breath CO,CO exposure,and Coburn model predictions in the U.S. EPA Washington-Denver (CO) study

The U.S. EPA studied the carbon monoxide (CO) exposures and resulting breath CO concentrations of 625 non-smoking persons in Washington, D.C., and 454 non-smokers in Denver, CO, in the winter of 1982–83. Mean population-weighted breath concentrations were 5.1 ± 0.2 (SE) ppm in Washington and 7.2 ± 0.2 ppm in Denver. These values were correlated with the preceding personal air CO exposures (Spearman rank correlation coefficient r_s > 0.5, P < 0.0001) but not with the outdoor concentrations (r_s < 0.2). However, the breath measurements did not agree very closely with the personal exposures according to the current (Coburn) model relating alveolar CO to ambient CO. One reason for the discrepancy may have been the slight observed negative bias displayed by the personal monitors. A method of using the breath measurements to arrive at an improved estimate of personal exposures has been developed and applied. The method leads to an upward revision of exposure estimates: about 10% of the Washington target population of 1.22 million non-smokers are estimated to have exceeded the EPA 8-h ambient standard of 9 ppm during the winter of 1982–83, well above the 3.5% indicated by the personal monitor measurements.     

Accuracy Assessment of EPA Protocol Gases Purchased In 1991

ABSTRACT

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

Environmental Issues—Persistent Problems and Emerging Challenges

Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10^-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10^-5 based on average values.     

The Effect of Water Vapor on Ozone Synthesis in the Photo-oxidation of Alpha-pinene

A study of the effect of water vapor on the photochemical system NO₂ + alphapinene + hv was conducted. A Hotpack Environmental Room was used as a constant temperature chamber, a bank of ultraviolet and fluorescent lamps as a source of simulated solar radiation, and a 150-liter FEP Teflon bag as a reaction vessel. Representative concentrations of 10 pphm NO₂ and 50 pphm alphapinene were used in a 3 × 2 × 2 factorial design where absolute humidities of 0.0000, 0.0090, 0.01 80 g H₂O/g dry air were varied.

Matheson zero air was passed through a clean air train and used as the diluent. Nitrogen dioxide was added to the reaction mixture by a permeation tube, and water and alpha-pinene by evaporation techniques.

Variables measured as a function of time over a 2-hour irradiation period were total oxidants (Mast Ozone Meter), condensation nuclei (General Electric Small Particle Detector), ozone (Regener Chemiluminescent Ozone Meter), nitrogen dioxide and nitric oxide (Technicon Autoanalyzer), and alpha-pinene (Perkin- Elmer Model 800 gas chromatograph).

Upon irradiation, systems containing nitrogen dioxide and alpha-pinene formed oxidants, ozone, condensation nuclei, and nitric oxide. Based on the differences between simultaneous oxidant and ozone measurements, the formation of peroxide- like compounds may be inferred. During the course of the irradiation, nitrogen dioxide and alpha-pinene were consumed. The concentration-time profiles of all variables were characteristic of those exhibited by typical photochemical smog systems.

An effect of water vapor on the systems studied was demonstrated. Increasing humidity decreased net mean/time oxidant and ozone production and net maximum condensation nuclei production. These effects were significant at a 0.05 confidence level. Effects of water on average mean/time NO₂, NO, and alphapinene concentrations were insignificant at this level. The oxidant to ozone ratio was found to decrease with increasing humidity.

The significant decreases in net oxidant and ozone production and NO₂ consumption with increasing water vapor concentration in systems of nitrogen dioxide alone, suggests that water manifests an effect on pertinent inorganic reactions, and the data also suggest additional water participation in the organic reactions.     

Chemical reactivities of ambient air samples in three Southern California communities

The potential adverse health effects of PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) and vapor samples from three communities that neighbor railyards, Commerce (CM), Long Beach (LB), and San Bernardino (SB), were assessed by determination of chemical reactivities attributed to the induction of oxidative stress by air pollutants. The assays used were dithiothreitol (DTT)- and dihydrobenzoic acid (DHBA)-based procedures for prooxidant content and a glyceraldehyde-3-phosphate dehydrogenase (GAPDH) assay for electrophiles. Prooxidants and electrophiles have been proposed as the reactive chemical species responsible for the induction of oxidative stress by air pollution mixtures. The PM_2.5 samples from CM and LB sites showed seasonal differences in reactivities, with higher levels in the winter, whereas the SB sample differences were reversed. The reactivities in the vapor samples were all very similar, except for the summer SB samples, which contained higher levels of both prooxidants and electrophiles. The results suggest that the observed reactivities reflect general geographical differences rather than direct effects of the railyards. Distributional differences in reactivities were also observed, with PM_2.5 fractions containing most of the prooxidants (74–81%) and the vapor phase most of the electrophiles (82–96%). The high levels of the vapor-phase electrophiles and their potential for adverse biological effects point out the importance of the vapor phase in assessing the potential health effects of ambient air.

Implications:?PM_2.5 and its corresponding vapor phase, containing semivolatile organics, were collected in three communities in the Los Angeles Basin and examined with toxicologically relevant chemical assays. The PM_2.5 phase contained most of the prooxidants and the vapor phase contained most of the electrophiles, whose content was highest in summer samples from a receptor site that reflected greater photochemical processing of the air parcel during its transport. As electrophiles initiate both adverse and adaptive responses to foreign substances by biological systems, their presence in the vapor phase emphasizes the importance of this phase in the overall health effects of ambient air.     

The effect of humidity and state of water surfaces on deposition of aerosol particles onto a water surface

Deposition processes of particles with dry diameter larger than about 10 μm are dominated by gravitational settling, while molecular diffusion and Brownian motion predominate the deposition processes of particles smaller than 0.1 μm in dry diameter. Many air pollution derived elements exhibit characteristics common to sub-micron particles. The objective of the present study is to examine the effects of meteorological conditions within the turbulent transfer layer on the deposition velocity of particles with dry diameter between 0.1 and 1 μm. It is for these sub-micron particles that particle growth by condensation in the deposition layer, the broken water surface effect and the enhanced transfer process due to atmospheric turbulence in the turbulent transfer layer play important roles in controlling the particle deposition velocity. Results of the present study show that the `dry air’ assumption of Williams’ model is unrealistic. Effects of ambient air relative humidity and water surface temperature cannot be ignored in determining the deposition velocity over a water surface. Neglecting effects of ambient air relative humidity and water surface temperature will result in defining atmospheric stability incorrectly. It is found that the largest effect of air relative humidity on deposition velocity occurs at an air–water temperature difference corresponding to the point of `displaced neutral stability'. For a given wind speed of U=5 m s⁻¹ the additive effects of water surface temperature, T_w, changes from 5 to 25°C and ambient air relative humidity variations from 85 to 60%, respectively, lead to a maximum difference in v_d of about 20%. For a higher wind speed of 10 m s⁻¹, however, the corresponding change in v_d reduces to less than 5%. This is further confirmation that wind speed is one of the strongest variables that governs the magnitude of v_d. The present study also found that the broken surface transfer coefficient, k_bs, given as a multiple of the smooth surface transfer coefficient, k_ss, is physically more meaningful than assigning it a constant value independent of particle size. The method used in this study requires only a single level of atmospheric data coupled with the surface temperature measurement. The present method is applicable for determining deposition velocity not only at the conventional measurement height of 10 m but also at any other heights that are different from the measurement height.     

Concentration of tetrachloroethylene in indoor air at a former dry cleaner facility as a function of subsurface contamination: a case study

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE < or =2,600,000 parts per billion by volume (ppbv) and trichloroethylene < or =170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10(-6) based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10(-5) based on average values.     

Concentrations,atmospheric partitioning,and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin,North China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m³, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m³, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (K _p) and the subcooled liquid vapor pressure (P _L ⁰) and octanol–air partition coefficient (K _oa). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.     

A Model for Uptake of Pollutants by Vegetation

A mass transfer approach is used in developing a practical mathematical model of gaseous pollutant uptake by leaves in which a series of resistances is summed across a concentration difference. The body of information presented in this paper is directed to plant pathologists or physiologists in the field of vegetal-pollutant effects and to people interested in the natural removal of air pollutants by vegetation. Correlations are given to calculate the aerodynamic and the stomatal resistances to uptake, while both a qualitative investigation and quantitative estimates are made of the mesophyllic resistance. The factors which control the aerodynamic resistance, r_a, are leaf size and wind speed, while the leaf physiology is the determinant of the stomatal resistance, r_s . It is noted that the chemical reaction rate and pollutant diffusivity in the mesophyll control the mesophyllic resistance, r_m, though the overall gas phase mesophyllic resistance, Hr_m, is strongly a function of pollutant solubility in water. Finally, the overall model is compared to earlier experimental work on vegetal uptake of SO₂.     

Validity of Ambient Levels of Fine Particles as Surrogate for Personal Exposure to Outdoor Air Pollution—Results of the European EXPOLIS-EAS Study (Swiss Center Basel)

ABSTRACT

To evaluate the validity of fixed-site fine particle levels as exposure surrogates in air pollution epidemiology, we considered four indicator groups: (1) PM₂₅ total mass concentrations, (2) sulfur and potassium for regional air pollution, (3) lead and bromine for traffic-related particles, and (4) calcium for crustal particles. Using data from the European EXPOLIS (Air Pollution Exposure Distribution within Adult Urban Populations in Europe) study, we assessed the associations between 48-hr personal exposures and home outdoor levels of the indicators. Furthermore, within-city variability of fine particle levels was evaluated.

Personal exposures to PM_2.5 mass were not correlated to corresponding home outdoor levels (n = 44, r_{S (S)} =r o v ' Spearman (Sp) 0.07). In the group reporting neither relevant indoor sources nor relevant activities, personal exposures and home outdoor levels of sulfur were highly correlated (n = 40, r_Sp = 0.85). In contrast, the associations were weaker for traffic (Pb: n = 44, r_Sp = 0.53; Br: n = 44, r_Sp = 0.21) and crustal (Ca: n = 44, r_Sp = 0.12) indicators. This contrast is consistent with spatially homogeneous regional pollution and higher spatial variability of traffic and crustal indicators observed in Basel, Switzerland.

We conclude that for regional air pollution, fixed-site fine particle levels are valid exposure surrogates. For source-specific exposures, however, fixed-site data are probably not the optimal measure. Still, in air pollution epidemiology, ambient PM_2.5 levels may be more appropriate exposure estimates than total personal PM_2.5 exposure, since the latter reflects a mixture of indoor and outdoor sources.     

Assessment of the aerosol water content in urban atmospheric particles by the hygroscopic growth measurements in Sapporo,Japan

Aerosol water content (AWC) of urban atmospheric particles was investigated based on the hygroscopic growth measurements for 100 and 200 nm particles using a hygroscopicity tandem differential mobility analyzer in Sapporo, Japan in July 2006. In most of the humidogram measurements, presence of less and more hygroscopic mode was evident from the different dependence on relative humidity (RH). The volume of liquid water normalized by that of dry particle (V_w(RH)/V_dry) was estimated from the HTDMA data for 100 and 200 nm particles. The RH dependence of V_w(RH)/V_dry was well represented by a fitted curve with a hygroscopicity parameter κ_eff. The κ_eff values for 200 nm particles were in general higher than those for 100 nm particles, indicating a higher hygroscopicity of 200 nm particles. Based on the κ_eff values, the volume mixing ratios of water-soluble inorganic compounds (ammonium sulfate equivalent) were estimated to be on average 31% and 45% for 100 and 200 nm particles, respectively. The diurnal variation of κ_eff, with relatively higher values in the noontime and nighttime and lower values in the morning and evening hours, was observed for both particle sizes. The V_w(RH)/V_dry values under ambient RH conditions were estimated from κ_eff to range from 0.05 to 2.32 and 0.06 to 2.43 for 100 nm and 200 nm particles, respectively. The degree of correlation between κ_eff and V_w(RH)/V_dry at ambient RH suggests a significant contribution of the variation of κ_eff to atmospheric AWC in Sapporo.     

Measurement of methyl halides in the marine atmosphere

An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH₃Cl, CH₃Br, and CH₃I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH₃Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH₃Cl concentration amounted to as high as 1400 pptv and indicated that CH₃Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH₃Br and CH₃I, suggesting a common source in the area.     

Ozone Dosage-Crop Loss Function for Alfalfa: A Standardized Method for Assessing Crop Losses from Air Pollutants

Ozone dose-crop loss conversion functions for alfalfa (Medicago sativa, L. var. Moapa 69) yield reduction and defoliation were developed using standardized field plots within an ambient O₃ gradient in the South Coast Air Basin. Seasonal yields and defoliation values were tested with O₃ dose, average daily maximum temperature, average daily minimum temperature, and average daily relative humidity in regression analyses to determine significant functional relationships. Only the ambient O₃ dose variable was found to have a significant effect on alfalfa yield or defoliation (yield, r = –0.827, t-slope = 3.900**; defoliation, r = –0.890, t-slope = 5.190**). The ozone dose-crop loss conversion functions were calculated by converting the dose-response functions to dose-percent reduction functions.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.