Peter C. Andersen

Ultrasonic detector for high precision measurements of carbon dioxide.

A new instrument for monitoring atmospheric CO(2) has been developed based on the measurement of the speed of sound in air. The instrument uses a selective scrubber to yield highly precise and accurate measurements of CO(2) mixing ratios at ambient concentrations. The instrument has a precision of 0.3 ppmv (1σ) with a signal that is independent of pressure and requires a flow rate of only 30 mL/min. Laboratory measurements of atmospheric CO(2) showed excellent agreement with values obtained by nondispersive infrared absorption. The instrument has the advantage of collecting continuous, high-precision data every 25 s and can be modified for vertical profiling studies using kites, balloons, or light aircraft for the purpose of measuring landscape-scale fluxes.

NOx instrument intercomparison for laboratory biomass burning source studies and urban ambient measurements in Albuquerque, New Mexico

ABSTRACT Understanding nitrogen oxides (NOx = NO + NO2) measurement techniques is important as air-quality standards become more stringent, important sources change, and instrumentation develops. NOx observations are compared in two environments: source testing from the combustion of Southwestern biomass fuels, and urban, ambient NOx. The latter occurred in the urban core of Albuquerque, NM, at an EPA NCORE site during February–March 2017, a relatively clean photochemical environment with ozone (O3) <60 ppb for all but 6 hr. We compare two techniques used to measure NOx in biomass smoke during biomass burning source testing: light absorption at 405 nm and a traditional chemiluminescence monitor. Two additional oxides of nitrogen techniques were added in urban measurements: a cavity attenuated phase shift instrument for direct NO2, and the NOy chemiluminescence instrument (conversion of NOy to NO by molybdenum catalyst). We find agreement similar to laboratory standards for NOx, NO2, and NO comparing all four instruments (R2 > 0.97, slopes between 0.95 and 1.01, intercepts < 2 ppb for 1-hr averages) in the slowly varying ambient setting. Little evidence for significant interferences in NO2 measurements was observed in comparing techniques in late-winter urban Albuquerque. This was also confirmed by negligible NOz contributions as measured with an NOy instrument. For the rapidly varying (1-min) higher NOx concentrations in biomass smoke source testing, larger variability characterized chemiluminescence and absorption instruments. Differences between the two instruments were both positive and negative and occurred for total NOx, NO, and NO2. Nonetheless, integrating the NOx signals over an entire burn experiment and comparing 95 combustion experiments, showed little evidence for large systematic influences of possible interfering species biasing the methods. For concentrations of <2 ppm, a comparison of burn integrated NOx, NO2, and NO yielded slopes of 0.94 to 0.96, R2 of 0.83 to 0.93, and intercepts of 8 to 25 ppb. We attribute the latter, at least in part, to significant noise particularly at low NOx concentrations, resulting from short averaging times during highly dynamic lab burns. Discrepancies between instruments as indicated by the intercepts urge caution with oxides of nitrogen measurements at concentrations <50 ppb for rapidly changing conditions. Implications: Multiple NOx measurement methods were employed to measure NOx concentrations at an EPA NCORE site in Albuquerque, NM, and in smoke produced by the combustion of Southwestern biomass fuels. Agreement shown during intercomparison of these NOx techniques indicated little evidence of significant interfering species biasing the methods in these two environments. Instrument agreement is important to understand for accurately characterizing ambient NOx conditions in a range of environments.

Portable Ozone Calibration Source Independent of Changes in Temperature,Pressure and Humidity for Research and Regulatory Applications

A highly portable ozone (O3) 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 O3scrubbed 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 O3 calibrator has a response time for step changes in output ozone mixing ratio of < 30 s and precision (σp) of 0.4 % of the output mixing ratio for 10 s measurements (e.g., σp =±0.4 ppb for 100 ppb of O3). 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.