Measurement of microenvironmental ozone concentrations in Durham, North Carolina, using a 2B Technologies 205 Federal Equivalent Method monitor and an interference-free 2B Technologies 211 monitor.

UNLABELLED: During August and September of 2012, researchers conducted a microenvironmental (ME) monitoring study in Durham, North Carolina, using two 2B Technologies O3 monitors: a dual-beam model 205 Federal Equivalent Method (FEM) 254 nm photometer and a newly developed model 211 interference-free dual-beam photometer. The two monitors were mounted in a wheeled, fan-cooled suitcase together with a battery, a disposable N2O cartridge for the model 211 monitor and filtered sample lines. A scripted technician made paired O3 measurements in a variety of MEs within 2 miles of a fixed-site FEM O3 photometer at the Durham National GuardArmory. The ratio of the 211 to Armory O3 concentrations tended to be lowest (<0.3) for 45 indoor MEs and highest (>0.8) for 104 outdoor MEs. The mean values of the ratio for in-vehicle MEs tended to fall between 0.2 and 0.7--the mean for all 27 in-car tests was 0.3. The ratio values for indoor MEs tended to be higher when the enclosure was well ventilated. The outdoor ratios tended to be lower when the measurement was made downwind of nearby roadways, likely due to exhaust NO. The in-vehicle ratios tended to be larger with windows open than closed; the smallest occurred with closed windows, active air conditioning, and vent recirculation. The 205 - 211 measurement differences were generally small, with 94% of the 176 sample differences below 5 ppb. Five differences were above 10 ppb with the largest values (173.9 and 63.6 ppb) occurring inside a violin repair shop. Roadway proximity tended to increase the differences for outdoor locations. The largest in-vehicle difference (6 ppb) occurred at a convenience store service station. As addressed in regulatory models, such differences may reduce estimated population O3 exposure by 30-50% in indoor and in-vehicle MEs where individuals spend more than 80% of their time. IMPLICATIONS: Computer models used to estimate exposures of human populations-such as the Air Pollution Exposure Model (APEX) developed by the U.S. Environmental Protection Agency-can be improved by use of direct microenvironmental (ME) measurement comparisons to nearby fixed-site monitors used for determining regulatory compliance. Simultaneous measurements made by model 211 and model 205 ozone monitors in a variety of MEs indicated that Federal Equivalent Method photometers similar to the model 205 may read high in the presence of various interferences associated with indoor sources and motor vehicles, increasing modeled exposures in such environments by 20-100%.

Concentrations of mobile source air pollutants in urban microenvironments.

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO2), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO(x)), particulate matter (< 2.5 microm diameter; PM2.5) mass, ultrafine particle (UFP; < 100 nm diameter) number black carbon (BC), speciated HAPs (e.g, benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O3) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs. Implications: Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.

Field testing of new-technology ambient air ozone monitors.

UNLABELLED: Multibillion-dollar strategies control ambient air ozone (O3) levels in the United States, so it is essential that the measurements made to assess compliance with regulations be accurate. The predominant method employed to monitor O3 is ultraviolet (UV) photometry. Instruments employ a selective manganese dioxide or heated silver wool "scrubber" to remove O3 to provide a zero reference signal. Unfortunately, such scrubbers remove atmospheric constituents that absorb 254-nm light, causing measurement interference. Water vapor also interferes with the measurement under some circumstances. We report results of a 3-month field test of two new instruments designed to minimize interferences (2B Technologies model 211; Teledyne-API model 265E) that were operated in parallel with a conventional Thermo Scientific model 49C O3 monitor. The field test was hosted by the Houston Regional Monitoring Corporation (HRM). The model 211 photometer scrubs O3 with excess nitric oxide (NO) generated in situ by photolysis of added nitrous oxide (N2O) to provide a reference signal, eliminating the need for a conventional O3 scrubber. The model 265E analyzer directly measures O3-NO chemiluminescence from added excess NO to quantify O3 in the sample stream. Extensive quality control (QC) and collocated monitoring data are assessed to evaluate potential improvements to the accuracy of O3 compliance monitoring. IMPLICATIONS: Two new-technology ozone monitors were compared with a conventional monitor under field conditions. Over 3 months the conventional monitor reported more exceedances of the current standard than the new instruments, which could potentially result in an area being misjudged as "nonattainment." Instrument drift can affect O3 data accuracy, and the same degree of drift has a proportionally greater compliance effect as standard stringency is increased. Enhanced data quality assurance and data adjustment may be necessary to achieve the improved accuracy required to judge compliance with tighter standards.

A re-examination of ambient air ozone monitor interferences.

Attaining the National Ambient Air Quality Standard (NAAQS) for ozone (O3) could cost billions of dollars nationwide. Attainment of the NAAQS is judged on O3 measurements made by the Federal Reference Method (FRM), ethylene chemiluminescence, or a Federal Equivalent Method (FEM), predominantly ultraviolet (UV) absorption. Starting in the 1980s, FRM monitors were replaced by FEMs so that today virtually all monitoring in the United States uses the UV methodology. This report summarizes a laboratory and collocated ambient air monitoring study of interferences in O3 monitors. Potential interferences examined in the laboratory included water vapor, mercury, o-nitrophenol, naphthalene, p-tolualdehyde, and mixed reaction products from smog chamber simulations of urban atmospheric photochemistry. UV absorption O3 monitors modified for humidity equilibration were also collocated with UV FEM O3 monitors at six sites in Houston, TX, during the 2007 summer O3 season. The results suggest that humidity and interfering species can positively bias (overestimate) O3 measured by FEM monitors used to determine compliance with the O3 standards. The results also suggest that humidity equilibration can mitigate this bias.

Field evaluations of newly available "interference-free" monitors for nitrogen dioxide and ozone at near-road and conventional National Ambient Air Quality Standards compliance sites.

Long-standing measurement techniques for determining ground-level ozone (O3) and nitrogen dioxide (NO2) are known to be biased by interfering compounds that result in overestimates of high O3 and NO2 ambient concentrations under conducive conditions. An increasing near-ground O3 gradient (NGOG) with increasing height above ground level is also known to exist. Both the interference bias and NGOG were investigated by comparing data from a conventional Federal Equivalent Method (FEM) O3 photometer and an identical monitor upgraded with an "interference-free" nitric oxide O3 scrubber that alternatively sampled at 2 m and 6.2 m inlet heights above ground level (AGL). Intercomparison was also made between a conventional nitrogen oxide (NOx) chemiluminescence Federal Reference Method (FRM) monitor and a new "direct-measure" NO2 NOx 405 nm photometer at a near-road air quality measurement site. Results indicate that the O3 monitor with the upgraded scrubber recorded lower regulatory-oriented concentrations than the deployed conventional metal oxide-scrubbed monitor and that O3 concentrations 6.2 m AGL were higher than concentrations 2.0 m AGL, the nominal nose height of outdoor populations. Also, a new direct-measure NO2 photometer recorded generally lower NO2 regulatory-oriented concentrations than the conventional FRM chemiluminescence monitor, reporting lower daily maximum hourly average concentrations than the conventional monitor about 3 of every 5 days. IMPLICATIONS: Employing bias-prone instruments for measurement of ambient ozone or nitrogen dioxide from inlets at inappropriate heights above ground level may result in collection of positively biased data. This paper discusses tests of new regulatory instruments, recent developments in bias-free ozone and nitrogen dioxide measurement technology, and the presence/extent of a near-ground O3 gradient (NGOG). Collection of unbiased monitor inlet height-appropriate data is crucial for determining accurate design values and meeting National Ambient Air Quality Standards.

Continuous monitoring of particle emissions during showering.

Particle formation from showering may be attributed to dissolved mineral aerosols remaining after evaporation of micron-sized satellite droplets produced by the showerhead or from splashing of larger shower water droplets on surfaces. Duplicate continuous particle monitors measured particle size distributions in a ventilated residential bathroom under various showering conditions, using a full-size mannequin in the shower to simulate splashing effects during showering. Particle mass concentrations were estimated from measured shower particle number densities and used to develop emission factors for inhalable particles. Emission source strengths of 2.7-41.3 microg/ m3/min were estimated under the various test conditions using residential tap water in Columbus, OH. Calculated fine particulate matter (PM2.5) concentrations in the bathroom reached several hundred micrograms per cubic meter; calculated coarse particulate matter (PM10) levels approached 1000 microg/m3. Rates of particle formation tended to be highest for coarse shower spray settings with direct impact on the mannequin. No consistent effects of water temperature, water pressure, or spray setting on overall emission rates were apparent, although water temperature and spray setting did have an effect when varied within a single shower sampling run. Salt solutions were injected into the source water during some tests to assess the effects of total dissolved solids on particle emission rates. Injection of salts was shown to increase the PM2.5 particle formation rate by approximately one third, on average, for a doubling in tap water-dissolved solids content; PM10 source strengths approximately doubled under these conditions, because very few particles >10 microm were formed.

High-end exposure relationships of volatile air toxics and carbon monoxide to community-scale air monitoring stations in Atlanta, Chicago, and Houston.

Evaporative and exhaust mobile source air toxic (MSAT) emissions of total volatile organic compounds, carbon monoxide, BTEX (benzene, toluene, ethylbenzene, and xylenes), formaldehyde, acetaldehyde, butadiene, methyl tertiary butyl ether, and ethanol were measured in vehicle-related high-end microenvironments (ME) under worst-case conditions plausibly simulating the >99th percentile of inhalation exposure concentrations in Atlanta (baseline gasoline), Chicago (ethanol-oxygenated gasoline), and Houston (methyl tertiary butyl either-oxygenated gasoline) during winter and summer seasons. High-end MSAT values as ratios of the corresponding measurements at nearby air monitoring stations exceeded the microenvironmental proximity factors used in regulatory exposure models, especially for refueling operations and MEs under reduced ventilation. MSAT concentrations were apportioned between exhaust and evaporative vehicle emissions in Houston where methyl tertiary butyl ether could be used as a vehicle emission tracer. With the exception of vehicle refueling operations, the results indicate that evaporative emissions are a minor component of high-end MSAT exposure concentrations.

Potential interference bias in ozone standard compliance monitoring.

The U.S. Environmental Protection Agency has established a federal reference method (FRM) for ozone (O3) and allowed for designation of federal equivalent methods (FEMs). However, the ethylene-chemiluminescence FRM for O3 has been replaced by the UV photometric FEM by most state and local monitoring agencies because of its relative ease of operation. Accumulating evidence indicates that the FEM is prone to bias under the hot, humid, and stagnant conditions conducive to high O3 formation. This bias may lead to overreporting hourly O3 concentrations by as much as 20-40 ppb. Measurement bias is caused by contamination of the O3 scrubber, a problem that is not detected by dry air calibration. An adequate wet test has not been codified, although a procedure has been proposed for agency consideration. This paper includes documentation of laboratory tests quantifying specific interferant responses, collocated ambient FRM/FEM monitoring results, and smog chamber comparisons of the FRM and FEMs with alternative scrubber designs. As the numbers of reports on monitor interferences have grown, interested parties have called for agency recognition and correction of these biases.

Frequency of open windows in motor vehicles under varying temperature conditions: a videotape survey in Central North Carolina during 2001.

Air pollution exposures in the motor vehicle cabin are significantly affected by air exchange rate, a function of vehicle speed, window position, vent status, fan speed, and air conditioning use. A pilot study conducted in Houston, Texas, during September 2000 demonstrated that useful information concerning the position of windows, sunroofs, and convertible tops as a function of temperature and vehicle speed could be obtained through the use of video recorders. To obtain similar data representing a wide range of temperature and traffic conditions, a follow-up study was conducted in and around Chapel Hill, North Carolina at five sites representing a central business district, an arterial road, a low-income commercial district, an interstate highway, and a rural road. Each site permitted an elevated view of vehicles as they proceeded through a turn, thereby exposing all windows to the stationary camcorder. A total of 32 videotaping sessions were conducted between February and October 2001, in which temperature varied from 41 degrees F to 93 degrees F and average vehicle speed varied from 21 to 77 mph. The resulting video tapes were processed to create a vehicle-specific database that included site location, date, time, vehicle type, vehicle color, vehicle age, window configuration, number of windows in each of three position categories (fully open, partially open, and closed), meteorological factors, and vehicle speed. Of the 4715 vehicles included in the database, 1905 (40.4%) were labeled as "open," indicating a window, sunroof, or convertible top was fully or partially open. Stepwise linear regression analyses indicated that "open" window status was affected by wind speed, relative humidity, vehicle speed, cloud cover, apparent temperature, day of week, time of day, vehicle type, vehicle age, vehicle color, number of windows, sunroofs, location, and air quality season. Open windows tended to occur less frequently when relative humidity was high, apparent temperature (a parameter incorporating wind chill and heat index) was below 50 degrees F, or the vehicle was relatively new. Although the effects of the identified parameters were relatively weak, they are statistically significant and should be considered by researchers attempting to model vehicle air exchange rates.

Determining the frequency of open windows in motor vehicles: a pilot study using a video camera in Houston, Texas during high temperature conditions.

Researchers have developed a variety of computer-based models to estimate population exposure to air pollution. These models typically estimate exposures by simulating the movement of specific population groups through defined microenvironments. Exposures in the motor vehicle microenvironment are significantly affected by air exchange rate, which in turn is affected by vehicle speed, window position, vent status, and air conditioning use. A pilot study was conducted in Houston, Texas, during September 2000 for a specific set of weather, vehicle speed, and road type conditions to determine whether useful information on the position of windows, sunroofs, and convertible tops could be obtained through the use of video cameras. Monitoring was conducted at three sites (two arterial roads and one interstate highway) on the perimeter of Harris County located in or near areas not subject to mandated Inspection and Maintenance programs. Each site permitted an elevated view of vehicles as they proceeded through a turn, thereby exposing all windows to the stationary video camera. Five videotaping sessions were conducted over a two-day period in which the Heat Index (HI)-a function of temperature and humidity-varied from 80 to 101 degrees F and vehicle speed varied from 30 to 74 mph. The resulting videotapes were processed to create a master database listing vehicle-specific data for site location, date, time, vehicle type (e.g., minivan), color, window configuration (e.g., four windows and sunroof), number of windows in each of three position categories (fully open, partially open, and closed), HI, and speed. Of the 758 vehicles included in the database, 140 (18.5 percent) were labeled as "open," indicating a window, sunroof, or convertible top was fully or partially open. The results of a series of stepwise linear regression analyses indicated that the probability of a vehicle in the master database being "open" was weakly affected by time of day, vehicle type, vehicle color, vehicle speed, and HI. In particular, open windows occurred more frequently when vehicle speed was less than 50 mph during periods when HI exceeded 99.9 degrees F and the vehicle was a minivan or passenger van. Overall, the pilot study demonstrated that data on factors affecting vehicle window position could be acquired through a relatively simple experimental protocol using a single video camera. Limitations of the study requiring further research include the inability to determine the status of the vehicle air conditioning system; lack of a wide range of weather, vehicle speed, and road type conditions; and the need to exclude some vehicles from statistical analyses due to ambiguous window positions.

A pilot study using scripted ventilation conditions to identify key factors affecting indoor pollutant concentration and air exchange rate in a residence.

A pilot study was conducted using an occupied, single-family test house in Columbus, OH, to determine whether a script-based protocol could be used to obtain data useful in identifying the key factors affecting air-exchange rate (AER) and the relationship between indoor and outdoor concentrations of selected traffic-related air pollutants. The test script called for hourly changes to elements of the test house considered likely to influence air flow and AER, including the position (open or closed) of each window and door and the operation (on/off) of the furnace, air conditioner, and ceiling fans. The script was implemented over a 3-day period (January 30-February 1, 2002) during which technicians collected hourly-average data for AER, indoor, and outdoor air concentrations for six pollutants (benzene, formaldehyde (HCHO), polycyclic aromatic hydrocarbons (PAH), carbon monoxide (CO), nitric oxide (NO), and nitrogen oxides (NO(x))), and selected meteorological variables. Consistent with expectations, AER tended to increase with the number of open exterior windows and doors. The 39 AER values measured during the study when all exterior doors and windows were closed varied from 0.36 to 2.29 h(-1) with a geometric mean (GM) of 0.77 h(-1) and a geometric standard deviation (GSD) of 1.435. The 27 AER values measured when at least one exterior door or window was opened varied from 0.50 to 15.8 h(-1) with a GM of 1.98 h(-1) and a GSD of 1.902. AER was also affected by temperature and wind speed, most noticeably when exterior windows and doors were closed. Results of a series of stepwise linear regression analyses suggest that (1) outdoor pollutant concentration and (2) indoor pollutant concentration during the preceding hour were the "variables of choice" for predicting indoor pollutant concentration in the test house under the conditions of this study. Depending on the pollutant and ventilation conditions, one or more of the following variables produced a small, but significant increase in the explained variance (R(2)-value) of the regression equations: AER, number and location of apertures, wind speed, air-conditioning operation, indoor temperature, outdoor temperature, and relative humidity. The indoor concentrations of CO, PAH, NO, and NO(x) were highly correlated with the corresponding outdoor concentrations. The indoor benzene concentrations showed only moderate correlation with outdoor benzene levels, possibly due to a weak indoor source. Indoor formaldehyde concentrations always exceeded outdoor levels, and the correlation between indoor and outdoor concentrations was not statistically significant, indicating the presence of a strong indoor source.