G. Hübler

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NOy in the atmosphere

A catalytic reduction technique for the measurement of total reactive odd-nitrogen NOy in the atmosphere was evaluated in laboratory and field tests. NOy component species include NO, NO2, NO3, HNO3, N2O5, CH3COO2NO2(PAN), and particulate nitrate. The technique utilizes the reduction of the higher oxides to NO in reaction with CO on a metal catalyst and the subsequent detection of NO by chemiluminescence produced in reaction with O3. The efficiency and linearity of the conversion of the principal NOy species were examined for mixing ratios in the range of 0.1 to 100 parts per billion by volume (ppbv). Results of tests with Au, Ni, and stainless steel as the catalyst in the temperature range of 25–500°C showed Au to be the preferred catalyst. NH3, HCN, N2O, CH4, and various chlorine and sulfur compounds were checked as possible sources of NOy interference with the Au catalyst. The effects of pressure, O3, and H2O on NOy conversion were also examined. The results of the checks and tests in the laboratory showed the technique to be suitable for initial NOy measurements in the atmosphere. The technique was subsequently tested in ambient air at a remote ground-based field site located near Niwot Ridge, Colorado. The results of conversion and inlet tests made in the field and a summary of the NOy data are included in the discussion.

Emissions lifetimes and ozone formation in power plant plumes

The concept of ozone production efficiency (OPE) per unit NOx is based on photochemical models and provides a tool with which to assess potential regional tropospheric ozone control strategies involving NOx emissions reductions. An aircraft study provided data from which power plant emissions removal rates and measurement-based estimates of OPE are estimated. This study was performed as part of the Southern Oxidants Study-1995 Nashville intensive and focuses on the evolution of NOx, SO2, and ozone concentrations in power plant plumes during transport. Two approaches are examined. A mass balance approach accounts for mixing effects within the boundary layer and is used to calculate effective boundary layer removal rates for NOx and SO2 and to estimate net OPE. Net OPE is more directly comparable to photochemical model results than previous measurement-based estimates. Derived net production efficiencies from mass balance range from 1 to 3 molecules of ozone produced per molecule of NOx emitted. A concentration ratio approach provides an estimate of removal rates of primary emissions relative to a tracer species. This approach can be combined with emissions ratio information to provide upper limit estimates of OPE that range from 2 to 7. Both approaches illustrate the dependence of ozone production on NOx source strength in these large point source plumes. The dependence of total ozone production, ozone production efficiency, and the rate of ozone production on NOx source strength is examined. These results are interpreted in light of potential ozone control strategies for the region.

Climatologies of NOx and NOy: A comparison of data and models

Abstract Climatologies of tropospheric NOx (NO + NO2) and NOy (total reactive nitrogen: NOx + N03 + 2 × N2O5 + HNO2 + HNO3 + HNO4 + ClONO2 + PAN (peroxyacetylnitrate) + other organic ni trates) have been compiled from data previously published and, in most cases, publicly archived. Emphasis has been on non-urban measurements, including rural and remote ground sites, as well as aircraft data. Although the distribution of data is sparse, a compilation in this manner can begin to provide an understanding of the spatial and temporal distributions of these reactive nitrogen species. The cleanest measurements in the boundary layer are in Alaska, northern Canada and the eastern Pacific, with median NO mixing ratios below 10 pptv, NOx below 50 pptv, and NOy below 300 pptv. The highest NO values (greater than 1 ppbv) were found in eastern North America and Europe, with correspondingly high NOy (∼ 5 ppbv). A significantly narrower range of concentrations is seen in the free troposphere, particularly at 3–6 km, with NO typically about 10 pptv in the boreal summer. NO increases with altitude to ∼ 100 pptv at 9–12 km, whereas NOy does not show a trend with altitude, but varies between 100 and 1000 pptv. Decreasing mixing ratios eastward of the Asian and North American continents are seen in all three species at all altitudes. Model-generated climatologies of NOx and NOy from six chemical transport models are also presented and are compared with observations in the boundary layer and the middle troposphere for summer and winter. These comparisons test our understanding of the chemical and transport processes responsible for these species distributions. Although the model results show differences between them, and disagreement with observations, none are systematically different for all seasons and altitudes. Some of the differences between the observations and model results may likely be attributed to the specific meteorological conditions at the time that measurements were made differing from the model meteorology, which is either climatological flow from GCMs or actual meteorology for an arbitrary year. Differences in emission inventories, and convection and washout schemes in the models will also affect the calculated NOα and NOy distributions.

Measurements of Tropospheric OH Concentrations: A Comparison of Field Data with Model Predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earths surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×106 to 3.2×106 cm-3. Simultaneously we measured the concentrations of O3, H2O, NO, NO2, CH4, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O3 and NO2. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NOx concentrations. It is argued that additional, so far unidentified. HOx loss reactions must be responsible for that discrepancy.

Regional ozone from biogenic hydrocarbons deduced from airborne measurements of PAN, PPN, and MPAN

NOx-catalyzed production of ozone over large regions of North America and Europe is a serious air quality problem that often involves biogenic hydrocarbons, mainly isoprene. Peroxy-methacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed uniquely from isoprene-NOx photochemistry hence is an indicator of recent ozone production from isoprene. Presented here are the first airborne measurements of MPAN along with PAN (peroxyacetic nitric anhydride, CH3C(O)OONO2), PPN (peroxypropionic nitric anhydride, CH3CH2C(O)OONO2) and ozone measurements. Relationships between these species are used to estimate the contributions of anthropogenic and biogenic hydrocarbons (BHC) to regional tropospheric ozone production, providing direct evidence of ozone production from BHC-NOx photochemistry.

Trace gas composition of midlatitude cyclones over the western North Atlantic Ocean: A conceptual model

[1] Midlatitude cyclones provide the energy necessary for most of the trace gas transport from North America to the western North Atlantic Ocean (WNAO). These cyclones are composed of four primary airstreams: warm conveyor belt (WCB), cold conveyor belt (CCB), dry airstream (DA), and post cold front (PCF) airstream. This study is the first to present a conceptual model of the chemical composition of a midlatitude cyclone tracking from North America to the WNAO. The model, a composite of chemical measurements from several cyclones, establishes the fundamental relationships between large-scale chemical transport and midlatitude cyclone structure. It also separates the meteorological influences on airstream trace gas signatures from the influence of surface emissions heterogeneity and presents characteristic mixing ratios of ozone, CO, NOx, and NOy within the four types of airstream during late summer/early autumn. While cyclone track and surface emissions heterogeneity impact the median trace gas values within airstreams, the O3/CO and O3/NOy slopes remain fairly constant. Several characteristics of the conceptual model impact trace gas signatures, regardless of cyclone track: (1) the DA always advects stratospheric ozone into the middle and upper troposphere; (2) the WCB is a more favorable location for photochemical ozone production than the CCB or PCF; (3) the PCF originates to the northwest, is unaffected by wet deposition, and the sunny conditions may allow for some photochemical ozone production; (4) the CCB is generally cloudy and does not show signs of significant photochemical ozone production; (5) both the CCB and the WCB experience wet deposition resulting in little NOy export from the lower troposphere. INDEX TERMS: 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 3364 Meteorology and Atmospheric Dynamics: Synoptic-scale meteorology;

Measurements of PAN, PPN, and MPAN made during the 1994 and 1995 Nashville Intensives of the Southern Oxidant Study: Implications for regional ozone production from biogenic hydrocarbons

Isoprene and a variety of other reactive hydrocarbons are released in large quantities by vegetation in forested regions and are thought to participate in the NOx-catalyzed production of ozone, a serious air quality problem in North America and Europe [National Research Council, 1991]. The determination of the fraction of O3 formed from anthropogenic NOx and biogenic hydrocarbons (BHC) is a crucial step in the formulation of effective control strategies. Peroxymethacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed almost entirely from the atmospheric oxidation of isoprene in the presence of NOx and is an excellent indicator of recent ozone production from isoprene and therefore biogenic hydrocarbons. Measurements are presented here of MPAN, peroxyacetic nitric anhydride (PAN, CH3C(O)OONO2), peroxypropionic nitric anhydride (PPN, CH3CH2C(O)OONO2) and ozone from separate data sets acquired during the 1994 and 1995 Nashville intensive studies of the Southern Oxidant Study. It was found that PAN, a general product of HC-NOx photochemistry, could be well represented as a simple linear combination of contributions from BHC and anthropogenic hydrocarbon (AHC) chemistries as indicated by MPAN and PPN, respectively. The PAN:MPAN ratios found to be characteristic of BHC-dominated chemistry ranged from 6 to 10. The PAN:PPN ratios found to be characteristic of AHC-dominated chemistry ranged from 5.8 to 7.4. These BHC and AHC attributions were used to estimate the contributions of anthropogenic and biogenic hydrocarbons to regional tropospheric ozone production, and substantial BHC-O3 (50–60 ppbv) was estimated in cases where high NOx from power plants was present in areas of high BHC emission. This estimation method provides direct evidence of significant photochemical ozone production from the oxidation of biogenic hydrocarbons in the presence of NOx.

An overview of the Stratospheric‐Tropospheric Experiment: Radiation, Aerosols, and Ozone (STERAO)‐Deep Convection experiment with results for the July 10, 1996 storm

The Stratospheric-Tropospheric Experiment: Radiation, Aerosols and Ozone (STERAO)-Deep Convection Field Project with closely coordinated chemical, dynamical, electrical, and microphysical observations was conducted in northeastern Colorado during June and July of 1996 to investigate the production of NOx by lightning, the transport and redistribution of chemical species in the troposphere by thunderstorms, and the temporal evolution of intracloud and cloud-to-ground lightning for evolving storms on the Colorado high plains. Major observations were airborne chemical measurements in the boundary layer, middle and upper troposphere, and thunderstorm anvils; airborne and ground-based Doppler radar measurements; measurement of both intracloud (IC) and cloud-to-ground (CG) lightning flash rates and locations; and multiparameter radar and in situ observations of microphysical structure. Cloud and mesoscale models are being used to synthesize and extend the observations. Herein we present an overview of the project and selected results for an isolated, severe storm that occurred on July 10. Time histories of reflectivity structure, IC and CG lightning flash rates, and chemical measurements in the boundary layer and in the anvil are presented showing large spatial and temporal variations. The observations for one period of time suggest that limited mixing of environmental air into the updraft core occurred during transport from cloud base to the anvil adjacent to the storm core. We deduce that the most likely contribution of lightning to the total NOx observed in the anvil is 60–90% with a minimum of 45%. For the July 10 storm the NOx produced by lightning was almost exclusively from IC flashes with a ratio of IC to total flashes >0.95 throughout most of the storms lifetime. It is argued that in this storm and probably others, IC flashes can be major contributors to NOx production. Superposition of VHF lightning source locations on Doppler retrieved air motion fields for one 5 min time period shows that lightning activity occurred primarily in moderate updrafts and weak downdrafts with little excursion into the main downdraft. This may have important implications for the vertical redistribution of NOx resulting from lightning production, if found to be true at other times and in other storms.

Measurements of nitric oxide and nitrogen dioxide during the Mauna Loa Observatory Photochemistry Experiment

NO and NO2 were simultaneously measured by photolytic conversion / chemiluminescence techniques during the Mauna Loa Observatory Photochemistry Experiment (MLOPEX). The field site, located at an elevation of 3.4 km on the north side of the Mauna Loa Volcano, was subject to two airflow regimes which typically corresponded to upslope (marine boundary layer plus island sources) conditions during the day and downslope (middle free tropospheric) conditions at night to mid-morning. Median values of NOx (NOx = NO + NO2) were 37 and 31 pptv during upslope and downslope conditions, respectively, with the downslope measurements consistent with previous measurements made from aircraft in the middle free troposphere over the North Pacific. Although the difference in median NOx mixing ratios in the upslope and downslope regimes is small, the influence of island sources of NOx is apparent. Indeed, the median upslope values were approximately 2.5 times greater than measurements made previously in the remote marine boundary layer. The data have been examined according to downslope / free tropospheric and upslope air flow regimes for relationships between NOx and the various species that were measured simultaneously (e.g., peroxyacetyl nitrate (PAN), HNO3, NO3, NOy, O3, CO, and hydrocarbons). While positive correlations between NOx and O3 and PAN were typically observed in free tropospheric air, these correlations were considerably weaker than those observed during previous campaigns. This is likely primarily due to the lower sampling altitude during the MLOPEX study. NOx and dew point temperature were weakly anticorrelated in free tropospheric air masses. Linear correlations between NOx and the peroxides, formaldehyde, alkyl nitrates, and hydrocarbons were also weak in the free tropospheric air masses at the MLO. NOx/NOy was typically on the order of 0.1–0.2 in free tropospheric flow. Considerably higher values of NOx/NOy, were occasionally observed under upslope conditions. The NOx/NOy and HNO3/NOx values obtained under downslope conditions were similar to those previously obtained during aircraft measurements in the middle free troposphere over the northeast Pacific. On the whole, the downslope air masses sampled appear to be characteristic of well-aged, marine free tropospheric air, and this conclusion is supported by 10-day trajectory analyses.

NO signatures from lightning flashes

In situ measurements of cloud properties, NO, and other trace gases were made in active thunderstorms by two research aircraft. Concurrent measurements from a three-dimensional (3-D) VHF interferometer and the 2-D National Lightning Detection Network were used to determine lightning frequency and location. The CHILL Doppler radar and the NOAA-WP-3D Orion X band Doppler radar were also used to measure storm characteristics. Two case studies from the (STERAO) Stratosphere-Troposphere Experiments: Radiation, Aerosols, and Ozone project in northeastern Colorado during the summer of 1996 are presented. Narrow spikes (0.11–0.96 km across), containing up to 19 ppbv of NO, were observed in the storms. Most were located in or downwind of electrically active regions where the NO produced by lightning would be expected. However, it was difficult to correlate individual flashes with NO spikes. A simple model of the plume of NO from lightning is used to estimate NO production from the mean mixing ratio measured in these spikes. The estimates range from 2.0×1020 to 1.0×1022 molecules of NO per meter of flash length.