Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex‐LA 2010 campaign using the laser‐induced fluorescence‐fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero‐dimensional model using the Regional Atmospheric Chemical Mechanism‐2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.
Abstract. Attributing observed CO2 variations to human or natural cause is critical to deducing and tracking emissions from observations. We have used in situ CO2, CO, and planetary boundary layer height (PBLH) measurements recorded during the CalNex-LA (CARB et al., 2008) ground campaign of 15 May–15 June 2010, in Pasadena, CA, to deduce the diurnally varying anthropogenic component of observed CO2 in the megacity of Los Angeles (LA). This affordable and simple technique, validated by carbon isotope observations and WRF-STILT (Weather Research and Forecasting model – Stochastic Time-Inverted Lagrangian Transport model) predictions, is shown to robustly attribute observed CO2 variation to anthropogenic or biogenic origin over the entire diurnal cycle. During CalNex-LA, local fossil fuel combustion contributed up to ~50% of the observed CO2 enhancement overnight, and ~100% of the enhancement near midday. This suggests that sufficiently accurate total column CO2 observations recorded near midday, such as those from the GOSAT or OCO-2 satellites, can potentially be used to track anthropogenic emissions from the LA megacity.
Abstract. We present quantitative, fast time response measurements of formaldehyde (HCHO) onboard an aircraft using a Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) instrument. The HCHO measurement by PTR-MS is strongly humidity dependent and therefore airborne measurements are difficult and have not been reported. The PTR-MS instrument was run in the standard PTR-MS operating mode , where about 15 volatile organic compounds (VOCs) are measured together with HCHO onboard the NOAA WP-3 aircraft during the CalNex 2010 campaign in California. We compare the humidity dependence determined in the laboratory with in-flight calibrations of HCHO and calculate the HCHO mixing ratio during all flights using the results from both. The detection limit (S/N = 1) for HCHO was between 100 pptv in the dry free troposphere and 300 pptv in the humid marine boundary layer for a one second acquisition time every 17 s. The PTR-MS measurements are compared with HCHO measurements using a DOAS instrument and a Hantzsch monitor at a ground site in Pasadena. The PTR-MS agreed with the DOAS within the stated uncertainties and was just outside the uncertainties with the Hantzsch. We also compare HCHO enhancement ratios in the Los Angeles basin and in the free troposphere with literature values and find good agreement. The usefulness of the PTR-MS HCHO measurements in atmospheric observations is demonstrated by following an isolated anthropogenic plume. The photochemical productionCorrespondence to: C. Warneke (carsten.warneke@noaa.gov) of HCHO can be observed simultaneously with production of acetaldehyde and the photochemical degradation of aromatic compounds using the PTR-MS. The results show that PTR-MS seems a useful instrument to measure HCHO, but more inter-comparisons are needed.
[1] During the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May-June 2010, measurements of volatile organic compounds (VOCs) were performed in the Los Angeles (LA) basin onboard a NOAA research aircraft and at a ground site located in Pasadena. A weekday-weekend effect in ozone, caused by lower NO x emissions due to reduced diesel truck traffic in the weekends, has been previously observed in Los Angeles and other cities. Measurements in the Caldecott tunnel show that emission ratios of VOCs do not vary with the day of the week, but measurements during CalNex2010 show a VOC weekday-weekend effect through faster photochemical processing at lower ambient NO x mixing ratios. Ambient VOC enhancement ratios of long-lived species such as benzene are the same between weekdays and weekends, whereas enhancement ratios of short-lived species, such as trimethyl benzene, are up to a factor of three lower on weekends. Based upon the observed differences in VOC enhancement ratios to CO, we determine that photochemical processing was on average 65%-75% faster on weekends during CalNex2010, which indicates that ambient OH radical concentrations were larger by this factor causing the observed change in VOC composition. A box model calculation based on the Master Chemical Mechanism was used to verify the increase in photochemical processing in the weekends.
Abstract. The concentration of gases and aerosol particles have been measured at the mountain site of Altzomoni, 4010 m in altitude, located 60 km southeast of Mexico City, 50 km east of Puebla and 70 km northeast of Cuernavaca. The objective of this study was to evaluate the properties of gases and particles in the Regional Mixed Layer (RML) of Mexico's Megapolis. Altzomoni is generally above the RML from late evening until late morning at which time the arrival of the RML is marked by increasing concentrations of CO and aerosol particles that reach their maxima in midafternoon. The average diurnal cycles for fourteen days in March, 2006 were evaluated during which time the synoptic scale circulation had three principal patterns: from the east (E), southwest (SW) and west northwest (WNW). The original hypothesis was that air arriving from the direction of Mexico City would have much higher concentrations of anthropogenic gases and particles than air from Puebla or Cuernavaca, due to the relatively large differences in populations. In fact, not only were the average, maximum concentrations of CO and O 3 (0.3 and 0.1 ppmv) approximately the same for air originating from the WNW and E, but the average maximum concentrations of Peroxyacyl nitrates (PAN,PPN) and particle organic matter (POM) in air from the E exceeded those in air from the WNW.Comparisons of measurements from the mountain site with those made by aircraft during the same period, using the same type of aerosol mass spectrometer, show that the total were approximately the same from aircraft measurements made over Mexico City and when winds were from the east at the mountain site. In contrast 75% of the total aerosol mass at the mountain site was POM whereas over Mexico City the fraction of POM was less than 60%.The measurements suggest the occasional influence of emissions from the nearby volcano, Popocatepetl, as well as possible incursions of biomass combustion; however, the large concentrations of O 3 , PAN and POM suggest that secondary processes are the major source for these gases and particles. The similar concentrations in gases and particles when air is coming from the E and NWN raises the possibility of recirculation of air from Mexico City and the importance of this mechanism for impacting the regional air quality.
Attributing observed CO2 variations to human or natural cause is critical to deducing and tracking emissions from observations. We have used in situ CO2, CO, and planetary boundary layer height (PBLH) measurements recorded during the CalNex-LA (CARB et al., 2008) ground campaign of 15 May–15 June 2010, in Pasadena, CA, to deduce the diurnally varying anthropogenic component of observed CO2 in the megacity of Los Angeles (LA). This affordable and simple technique, validated by carbon isotope observations, is shown to robustly attribute observed CO2 variation to anthropogenic or biogenic origin. During CalNex-LA, local fossil fuel combustion contributed up to ~50 % of the observed CO2 enhancement overnight, and ~100 % during midday. This suggests midday column observations over LA, such as those made by satellites relying on reflected sunlight, can be used to track anthropogenic emissions
[1] Air quality simulations were performed for the Houston-Galveston-Brazoria area for springtime conditions in May and June of 2009. Meteorological parameters predicted by Weather Research and Forecasting (WRF) model, for which data assimilation with recursive objective analysis was performed, are well simulated most of the time. The Community Multiscale Air Quality (CMAQ) model driven by meteorology from WRF simulates ozone and many other trace species, including radical precursors such as HCHO and HONO, with a satisfactory agreement with observations. While CMAQ satisfactorily captures the daily variations of the OH radical, it sometimes underestimates its high daytime values. Concentrations of HO 2 are often underpredicted in polluted air masses and persistently severely underpredicted at low NO x conditions, when the Houston air is affected by marine air masses. In contrast, concentrations of H 2 O 2 and CH 3 OOH are almost always overpredicted by the model, the overprediction occurs frequently in the polluted air and occurs always when marine air is encountered. Those mispredictions are consistent despite day-to-day variations in meteorological conditions and emissions and bring into question current representation of radical-related chemistry in the model as radical production and recirculation in the model is overtaken by termination processes and creation of more stable compounds, such as H 2 O 2 and CH 3 OOH. Smaller model biases of H 2 O 2 and peroxides are associated with lower humidity. The relative importance of various photolysis processes as radical sources in the Houston atmosphere was also elucidated. Morning HO x formation is dominated by HONO while ozone contributes the most during midday. HONO contribution to HO x formation is more pronounced at the surface layer where most of it is formed, radical production from ozone is more important at elevated levels where higher concentrations of ozone are observed. Formaldehyde contributes up to 40% and also peaks during midday, but on days when high morning concentrations of formaldehyde are observed, its contribution to HO x in the morning exceeds that of ozone. Photolysis of H 2 O 2 is a minor contributor to radical levels.Citation: Czader, B. H., X. Li, and B. Rappenglueck (2013), CMAQ modeling and analysis of radicals, radical precursors, and chemical transformations,
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