Abstract. We describe and characterize a modular folded tubular photometer for making direct measurements of the concentrations of nitrogen dioxide (NO2) and specify how this method could be extended to measure other pollutants such as sulfur dioxide (SO2), ozone (O3), and black carbon particulate matter. Direct absorbance measurements using this photometer can be made across the spectral range from the ultraviolet (UV) to the near infrared. The absorbance cell makes use of modular components (tubular detection cells and mirror cubes) that allow construction of path lengths of up to 2 m or more while maintaining low cell volumes. The long path lengths and low cell volumes enable sensitive detection of ambient air pollutants down to low part-per-billion levels for gas species and aerosol extinctions down to 1 Mm−1, corresponding to ∼ 0.1 µg m−3 for black carbon particulates. Pressure equalization throughout the stages of the absorbance measurement is shown to be critical to accurate measurements of analyte concentrations. The present paper describes the application of this photometer to direct measurements of nitrogen dioxide (NO2) and the incorporation of design features that also enable measurement of nitric oxide (NO) in the same instrument. Excellent agreement for ambient measurements along an urban roadside was found for both NO2 and NO measured by the folded tubular photometer compared to existing standard techniques. Compared to commonly used methods for measurements of NOx species, the advantages of this approach include (1) an absolute quantification for NO2 based on the Beer–Lambert law, thereby greatly reducing the frequency at which calibrations are required; (2) the direct measurement of NO2 concentration without prior conversion to NO as is required for the commonly used chemiluminescence method; (3) the use of modular components that allow construction of absorbance detection cells of varying lengths for extending the dynamic range of concentrations that can be measured; (4) a more economical instrument than other currently available direct measurement techniques for NO2; and (5) the potential for simultaneous detection of additional species such as SO2, O3, and black carbon in the same instrument. In contrast to other commercially available direct NO2 measurements, such as cavity-attenuated phase-shift spectroscopy (CAPS), the folded tubular photometer also measures NO simultaneously in the same apparatus by quantitatively converting NO to NO2 with ozone, which is then detected by direct absorbance.

A new portable instrument has been developed that offers rapid detection of ozone at the ppb level for personal exposure monitoring. The Personal Ozone Monitor is based on the EPA Federal Reference Method of UV absorbance and has the advantage of being small (10 × 7.6 × 3.8 cm), light-weight (0.3 kg), low power (2.9 watts), and battery-operated. The instrument can be worn by an individual during normal daily activities because it is unaffected by humidity, physical orientation, temperature, and vibration. In order to eliminate any significant interference from water vapor, Nafion® tubing was installed before the detection cell, and the optical path was lined with quartz. A precision of 1.5 ppbv and limit of detection of 4.5 ppbv (S/N = 3) was demonstrated with the instrument making measurements every 10 seconds.

Abstract. A highly portable ozone (O 3 ) calibration source that can serve as a U.S. EPA level 4 transfer standard for the calibration of ozone analyzers is described and evaluated with respect to analytical figures of merit and effects of ambient pressure and humidity. Reproducible mixing ratios of ozone are produced by the photolysis of oxygen in O 3 -scrubbed ambient air by UV light at 184.9 nm light from a low-pressure mercury lamp. By maintaining a constant volumetric flow rate (thus constant residence time within the photolysis chamber), the mixing ratio produced is independent of both pressure and temperature and can be varied by varying the lamp intensity. Pulse width modulation of the lamp with feedback from a photodiode monitoring the 253.7 nm emission line is used to maintain target ozone mixing ratios in the range 30-1000 ppb. In order to provide a constant ratio of intensities at 253.7 and 184.9 nm, the photolysis chamber containing the lamp is regulated at a temperature of 40 • C. The resulting O 3 calibrator has a response time for step changes in output ozone mixing ratio of < 30 s and precision (σ p ) of 0.4 % of the output mixing ratio for 10 s measurements (e.g., σ p = ±0.4 ppb for 100 ppb of O 3 ). Ambient humidity was found to affect the output mixing ratio of ozone primarily by dilution of the oxygen precursor. This potential humidity interference could be up to a few percent in extreme cases but is effectively removed by varying the lamp intensity to compensate for the reduced oxygen concentration based on feedback from a humidity sensor.

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Abstract. A new solid-phase scrubber for use in conventional ozone (O 3 ) photometers was investigated as a means of reducing interferences from other UV-absorbing species and water vapor. It was found that when heated to 100-130 • C, a tubular graphite scrubber efficiently removed up to 500 ppb ozone and ozone monitors using the heated graphite scrubber were found to be less susceptible to interferences from water vapor, mercury vapor, and aromatic volatile organic compounds (VOCs) compared to conventional metal oxide scrubbers. Ambient measurements from a graphite scrubberequipped photometer and a co-located Federal equivalent method (FEM) ozone analyzer showed excellent agreement over 38 days of measurements and indicated no loss in the scrubber's ability to remove ozone when operated at 130 • C. The use of a heated graphite scrubber was found to reduce the interference from mercury vapor to ≤ 3 % of that obtained using a packed-bed Hopcalite scrubber. For a series of substituted aromatic compounds (ranging in volatility and absorption cross section at 253.7 nm), the graphite scrubber was observed to consistently exhibit reduced levels of interference, typically by factors of 2.5 to 20 less than with Hopcalite. Conventional solid-phase scrubbers also exhibited complex VOC adsorption and desorption characteristics that were dependent upon the relative humidity (RH), volatility of the VOC, and the available surface area of the scrubber. This complex behavior involving humidity is avoided by use of a heated graphite scrubber. These results suggest that heated graphite scrubbers could be substituted in most ozone photometers as a means of reducing interferences from other UV-absorbing species found in the atmosphere. This could be particularly important in ozone monitoring for compliance with the United States (U.S.) Clean Air Act or for use in VOC-rich environments such as in smog chambers and monitoring indoor air quality.