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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.

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RESUMO

Measurements of δ(13)CH4 and CH4 concentration were made at a field site in Four Corners, New Mexico (FC), where we observed large sustained CH4 enhancements (2-8 ppm peaks for hours) during nocturnal inversions. Potential sources of this large CH4 signal at FC include (1) fugitive emissions from coal mining and gas processing that are thermogenic and isotopically (13)C enriched relative to background atmosphere and (2) emissions from agriculture, ruminants, landfills, and coalbed biogenic methane that are(13)C depleted relative to background atmosphere. We analyze our measurements of methane concentration and δ(13)C during spring and summer of 2012 to identify fugitive methane sources. We find CH4 plumes that are both enriched and depleted in (13)C relative to CH4 in background air. Keeling plots show a continuum of δ(13)C source compositions between -40‰ and -60‰ that are consistent with thermogenic and biogenic sources. The Picarro Mobile Methane Investigator (PMMI), a mobile δ(13)CH4 instrument platform, was deployed in the spring of 2013 and used to verify the isotopic enrichment of coal bed methane in the region. We combine our results with meteorological data to spatially separate these sources in the Four Corners regions. Using CO and CO2 data, along with meteorological data, we propose that the high methane concentration events ([CH4] > 3.5 ppm) are from both thermogenic and biogenic methane released from coal beds.