Ozone Measurements in South Carolina Using Passive Samplers

Abstract

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography.

Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina.

Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 ± 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 ± 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 ± 6.3 ppb, n = 22).     

Measurement of Ozone Concentrations in Ambient Air Using a Badge-Type Passive Monitor

Abstract

A badge-type passive monitor was used to evaluate the effectiveness of four ozone trapping reagents for measuring O₃ concentrations in the air. These were sodium nitrite (NaNO₂), 3-methyl-2-benzothiazolinone acetone azine (MBTH), p-acetamidophenol (p-ATP), and indigo carmine. Experiments in an exposure chamber showed that only NaNO₂ and MBTH monitors gave sensitive and linear responses over realistic ranges of O₃ concentrations. When tested in ambient air, NaNO₂ and MBTH monitors with a single-layer diffusion barrier overestimated O₃ concentrations by a significant amount. This was largely canceled out in the NaNO₂ monitor by using a multi-layered diffusion barrier to combat wind turbulence effects. However it had almost no effect on the MBTH monitor, and it was found that NO₂ was a source of serious interference. We concluded that using the NaNO₂ monitor with an effective diffusion barrier can measure O₃ in ambient air with an accuracy of ±16%.     

High Volume Sampling: Errors Incurred during Passive Sample Exposure Periods

The current Federal EPA reference method for the determination of total suspended particulate matter (TSP) in the atmosphere is the high volume method (hi-vol).¹ The hi-vol sampler is normally operated for a 24 hr period by drawing air through an 8 X 10 in. glass fiber filter at an air sampling flow rate of between 40-60 cfm. TSP samples are presently collected in this manner every 6th day (61 samples/year). Results are used to determine compliance with existing National Primary Ambient Air Quality Standards for TSP (i.e., 260 µg/m³, maximum 24 hr average, not to be exceeded more than once a year; 75 µg/m³, annual geometric mean). However, when the sampling frequency is diminished to only 61 out of a possible 365 measurements each year, the degree of certainty associated with meeting these air quality standards is also decreased.^2,3 This partial sampling schedule also introduces other sampling errors. One such error caused by the exposure of the collection filter both prior and subsequent to the desired sampling day is the subject of the following discussion.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

A 13-Week Comparison of Passive and Continuous Ozone Monitors at Forested Sites in North-Central Pennsylvania

ABSTRACT

Ogawa passive O₃ samplers were used in a 13-week study (June 1-September 1, 1999) involving 11 forested and mountaintop sites in north-central Pennsylvania. Four of the sites were collocated with TECO model 49 O₃ analyzers. A significant correlation (p < 0.0001) was found for 24-hr average weekly O₃ concentrations between the two methodologies at the four sites with collocated monitors. As expected, there were positive relationships between increasing elevation of the sites and increasing O₃ concentrations. No O₃ exposure patterns were found on a west-to-east or south-to-north basis; however, the area known for lower O₃ exposures within a smaller subsection of the study area showed consistently lower O₃ exposures. Preliminary results regarding relationships of symptom responses within O₃-sensitive bioindicators are also presented with black cherry (Prunus serotina, Elirli.) and common milkweed (Asclepias syriaca, L.) showing clear evidence of increasing injury with increasing O₃ exposures. Due to the extremely dry conditions encountered in north-central Pennsylvania during the 1999 growing season, O₃-induced symptoms were sporadic and quite delayed until late-season rains during the latter portion of the observation period.     

Determination of Ozone in Outdoor and Indoor Environments Using Nitrite-Impregnated Passive Samplers Followed by Ion Chromatography

Abstract

An improved ion chromatographic (IC) method has been developed for the separation of nitrate in filter extracts in the presence of high concentrations of nitrite. This analytical method was successfully used for an indirect measurement of ozone (O₃) in outdoor and indoor air, following its collection using a nitrite-impregnated passive sampler. The limit of detection and the limit of quantification, using the modified IC method, were 6 μg l^-1 (3σ) and 20 μg l^-1 (10σ), respectively. Improved detection limits and low baseline noise were obtained with the use of eluent generator and high-capacity ion exchange column. The optimized method was used for assessing O₃ concentration in both indoor and outdoor environments of 28 child care centers (CCCs) located in different parts of Singapore. The O₃ concentrations ranged from 0.1 to 11.95 parts per billion (ppb) in indoor and from 3.2 to 21.7 ppb in outdoor environments during the study period. It was found that, among the CCCs investigated in this study, air-conditioned CCCs and those located in close proximity to traffic emissions had significantly lower O₃ concentrations indoors.     

Rationale for an Eight-Hour Ozone Standard

As part of the exposure assessment scheme for a community-based air pollution health effects study, 43 homes of study participants, located in two Houston neighborhoods, were monitored for weekly-average indoor formaldehyde levels by means of diffusion samplers. Consecutive 12-hour aldehyde sampling for one-week periods was conducted in 12 of the homes by means of pumps and impingers. In six houses where simultaneous monitoring with both methods occurred, good correlation between the results from the diffusion samplers and the standard impinger method was observed. Diffusion sampler precision was variable and lower than expected, and a small positive measurement bias could be inferred. The distribution of house-average indoor formaldehyde concentrations from diffusion monitoring was similar to that obtained during a previous housing survey in Houston, with concentrations in 19 percent of the homes exceeding 0.10 ppm. Formaldehyde levels in this group of conventional, mostly older homes could not be associated with smoking, cooking, home age or structure type. However, there was a statistically significant difference between mean indoor concentrations in the two neighborhoods.     

Ozone Transport

Elevated concentrations of ozone, often above the national ambient air quality standard for photochemical oxidants, have been measured in both urban and rural areas of Connecticut. One such episode took place on June 10, 1974. Ozone levels, after stabilizing at values slightly above the standard (i.e., 80 to 110 ppb; Connecticut generated ozone concentrations), rose sharply late in the afternoon reaching concentrations as high as 310 ppb (almost 4 times the standard) in Hartford. The trajectory of the air mass, which arrived in Hartford at the time of maximum O₃ occurence, had its origin in the metropolitan New York area during the early morning rush hour on the episode day. This illustrates that the advective transport of O₃ and O₃ precursors into Connecticut from New York are probably responsible for a significant portion (approximately two-thirds) of the elevated O₃ concentrations measured throughout Connecticut on days when winds are from the south-southwest direction. The fact that peak O₃ levels occur late in the afternoon, several hours after maximum sunlight intensity, reinforces the conclusion that excessive O₃ concentrations developed as O₃ and ozone precursors were generated in the vicinity of New York City and then drifted inland into Connecticut on the afternoon sea breeze.

It appears to be unrealistic to develop a hydrocarbon control strategy for Connecticut in order to meet the photochemical oxidant ambient air quality standard when O₃ and/or ozone precursors ad-vectively transported into the State cause oxidant levels to exceed the standard. The complete cessation of all anthropogenic hydrocarbon emissions in Connecticut would not necessarily assure that the standard would be attained here. The implication is that a regional (i.e., the eastern part of the United States) hydrocarbon control strategy is needed to reduce adequately ozone formation and transport so as to allow Connecticut to meet the current oxidant standard.     

Ozone exposure

Increased tropospheric ozone concentrations cause damage to both human health and the environment. To assess the exposure of forest areas and selected tree species to ozone, it is necessary to calculate the ozone exposure distribution. The present article describes the application of an ozone interpolation model to the calculation of the ozone exposure distribution in combination with forest inventory data. The exposure of forest regions to ozone was assessed by means of an AOT40 map (accumulated ozone exposure over a threshold of 40 ppb). The calculation was performed by hourly running of the model during the summer term and accumulation of the patterns that exceeded 40 ppb. The exposure of the primary Austrian tree species to ozone can be assessed due to the spatial relation of ozone exposure and tree species patterns. This spatial relation also allows the verification of assumptions concerning ozone-related tree damage.     

A Technique for Respirable Sampling

The purpose of this paper is to describe instrumentation to aerodynamically size suspended particulates found in ambient air and to summarize results of field testing utilizing the new technique.

A four-stage, multiorifice high-volume fractionating impactor with backup filter, which can be operated as a component of the standard high-volume sampler, collects particulate matter in five separate aerodynamic size ranges: 7 micrometer (μm) or larger, 3.3 to 7 μm, 2.0 to 3.3 μm, 1.1 to 2.0 μm, and 0.01 to 1.1 μm.

Comparative field tests utilizing duplicate sampling techniques were conducted to determine the feasibility of using the size fractionator on a routine basis in field operations. Verification of the actual particle size separation was not undertaken; however, earlier tests utilizing laboratory-generated aerosols have been performed with satisfactory results.

The results of field tests indicate that the fractionator can be used to determine the aerodynamic size distribution of particulate matter. A glass fiber surface with a pH of 11.0 was found to adsorb atmospheric acid gases during sampling and thus gave erroneous mass concentration results when compared to the standard high-volume sampler. Glass fiber filters with a pH of 6.5 eliminated the acid gas adsorption.     

Public Reaction to SIP Revisions for Ozone Reduction

ABSTRACT

This study utilized a biotrickling filter with blast-furnace slag packings (sizes = 20-40 mm; specific surface area = 120 m²/m³) to treat toluene in an air stream. Also studied were the effects of volumetric loading (L), nutrient addition, and superficial gas velocity (U_g) or gas retention time on toluene elimination capacity. Experimental results indicate that, for a test period of 121 days, with no excess biomass removal, toluene removal efficiencies of over 90% were obtained with U_g < 80 m/hr and L < 30 g/m³.hr. For a test period of 49 days, with U_g < 80 m/hr and L increased from 1.2 to 81 g/m³.hr, the absence of nutrient supplementation did not limit the toluene elimination capacity. Nutrients stored in the biofilm could adequately support the microbial activity for the toluene elimination. According to data regression, a simplified mass-transfer model is proposed, which correlates the contaminant concentration with the packing height or gas empty bed retention time. As verified, the model proposed herein can be applied to cases involving low influent contaminant concentrations or loadings to the extent that none or only a trace amount of the contaminant can be found in the recirculation liquid. Although small media with larger specific surface areas can achieve a better mass transfer, the problems of frequent backwashing and relatively greater gas resistance in using this type of media probably outweigh the advantages, particularly for full-scale systems that would not be watched as closely as laboratory test systems.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

Programmable Instrument for Controlling Atmospheric Sampling

The University of Arizona and the Pima County Air Pollution Control District conducted a comparison study of the following aerosol samplers: a standard high-volume sampler, a high-volume sampler fitted with a size selective inlet, and a dichotomous virtual impactor. Over sixty samples were collected with the colocated samplers during the first six months of 1981. The concentration (μg/m³) of suspended particulate matter and of sulfate was determined for all the samples, while the concentration of four lithophilic elements (Ca, Fe, Mg, and K) was determined on one third of the samples. Well-defined linear relationships for suspended particulate matter and sulfate were found to exist between each of the three sample collection methods over the concentrafion range encountered in this study. For these samples, there were significant differences in the particulate mass and large particle lithophilic element concentrations collected by each device. However, sulfate values obtained from the three samplers were in excellent agreement with each other. This suggests that the inlet collection efficiency for large particles differs significantly for these three sampling devices. Since the size selective inlet and the dichotomous virtual impactor samplers are each designed for collection of inhalable particles (particles of 15 μm aerodynamic diameter and smaller), they would have been expected to measure approximately equivalent particle mass concentrations. Thus, these differences are important to those interested in selecting a method for measuring airborne particle mass concentrations.     

Ozone and grosswetterlagen

Meteorological conditions have a decisive impact on surface ozone concentrations. In this study, an empirical model is used to explain the interdependence of ozone and grosswetterlagen. Different meteorological parameters such as air temperature, global solar radiation, relative humidity, wind direction and wind speed are used. Additional nitric oxide (NO) was taken as a representative for the emission situation and ozone maximum of the preceding day in order to evaluate the development of the photochemical situation. The dataset includes data collected over a period of three years (1992–1994) from three stations outside of Munich and one in the center of Munich. All values become variables by calculating means, sums or maxima of the basic dataset consisting of half-hour means. Seasonal periodicity of data is detected with Fourier analysis and eliminated by a division method after computing a seasonal index. The dataset is divided into three different grosswetterlagen groups, depending on main wind direction. One mostly cyclonic (westerly winds), onemixed (alternating winds) and one onlyanticyclonic (easterly winds). The last is completed with one summertime group including values from April to August. Factor analysis is performed for each group to obtain independent linear variable combinations. Overall, relative humidity is the dominant parameter, a typical value indicating meteorological conditions during a grosswetterlage. Linear multiple regression analysis is performed using the factors obtained to reveal how the ozone concentrations are explained in terms of meteorological parameters and NO. The results improve from cyclonic to anticyclonic grosswetterlagen in conformance with the increasing significance of photochemistry, indicated by the high solar radiation and high temperature, and the low relative humidity and low wind speed. The explained variance r² reaches its maximum with more than 50 % of the time in Munich center. This empirical model is applicable to the forecasting of local ozone maximum concentrations with a total standard error deviation of 8.5 to 12.8 % and, if ozone concentrations exceed 80 ppb, with a standard error deviation of 5.4 to 9.5 %.     

Ozone and grosswetterlagen

Meteorological conditions have a decisive impact on surface ozone concentrations. In this study, an empirical model is used to explain the interdependence of ozone and grosswetterlagen. Different meteorological parameters such as air temperature, global solar radiation, relative humidity, wind direction and wind speed are used. Additional nitric oxide (NO) was taken as a representative for the emission situation and ozone maximum of the preceding day in order to evaluate the development of the photochemical situation. The dataset includes data collected over a period of three years (1992–1994) from three stations outside of Munich and one in the center of Munich. All values become variables by calculating means, sums or maxima of the basic dataset consisting of half-hour means. Seasonal periodicity of data is detected with Fourier analysis and eliminated by a division method after computing a seasonal index. The dataset is divided into three different grosswetterlagen groups, depending on main wind direction. One mostly cyclonic (westerly winds), one mixed (alternating winds) and one only anticyclonic (easterly winds). The last is completed with one summertime group including values from April to August. Factor analysis is performed for each group to obtain independent linear variable combinations. Overall, relative humidity is the dominant parameter, a typical value indicating meteorological conditions during a grosswetterlage. Linear multiple regression analysis is performed using the factors obtained to reveal how the ozone concentrations are explained in terms of meteorological parameters and NO. The results improve from cyclonic to anticyclonic grosswetterlagen in conformance with the increasing significance of photochemistry, indicated by the high solar radiation and high temperature, and the low relative humidity and low wind speed. The explained variance r² reaches its maximum with more than 50 % of the time in Munich center. This empirical model is applicable to the forecasting of local ozone maximum concentrations with a total standard error deviation of 8.5 to 12.8 % and, if ozone concentrations exceed 80 ppb, with a standard error deviation of 5.4 to 9.5 %.     

Eight-Hour Ozone Trends at Sites in Lake Michigan Ozone Nonattainment Areas

ABSTRACT

Temperature-adjusted trends in 1-hr and 8-hr ozone averages were calculated for ten sites near Lake Michigan for 1980-1995. Results show that ozone trends declined similarly according to both metrics for sites on the west side of the lake. This suggests that the factors underlying the trends were similar. These factors include, among others, ozone control programs designed to address the 1-hr standard. Thus, these control programs may have been similarly effective in moving these sites toward compliance with the 8-hr standard.     

Data Analysis Procedures for the Ozone NAAQS Statistical Format

The Clear Air Act of 1970 established the authority to control hazardous air pollutants. Section 112 of the legislation requires the Administrator to publish, and from time to time revise, a list of hazardous air pollutants for which he intends to establish emission standards, and to establish emission standards for those pollutants. These national emission standards for hazardous air pollutants are commonly referred to as “NESHAP” standards. All of the NESHAP that have been promulgated as of April 1984 are summarized in the table which accompanies this article. Two types of references are included in the table. The first reference identifies the issue of the Federal Register in which the NESHAP is explained in detail. The second reference identifies the background information document (BID) which contains the technical and economic information developed to support the NESHAP.     

New and Improved Procedures for Gas Sampling and Analysis in the National Air Sampling Network

The NASN sampler for the collection of gaseous pollutants has been modified to increase its versatility and efficiency. Oxides of nitrogen are collected in bubblers employing a 70-100 μ frit with a collection efficiency of approximately 50% depending upon the frit porosity. Included in the sampler is a bubbler for the collection of aldehydes in which the aldehyde-MBTH complex is stable at least two weeks. This inert bubbler, which is constructed of polypropylene and Teflon, makes it possible for samples to be collected over the network and analyzed at a central laboratory. In addition, gaseous ammonia is collected in 0.1N H₂SO₄. This collecting system has an efficiency of greater than 85%. Low-level samples are analyzed automatically employing Nesslerization, whereas high-level samples from source emissions may be collected in indicating boric acid and titrated with 0.02N H₂SO₄. The sampler will accommodate either 50 or 100 ml polypropylene collecting tubes.