Ambient Air Measurements Research Articles

Polychlorinated Dibenzo-P-Dioxins and Dibenzofurans (PCDD/F) Measurements in Ambient Air over the Northern Poland

Polychlorinated Dibenzo-P-Dioxins and Dibenzofurans (PCDD/F) Measurements in Ambient Air over the Northern Poland

Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from fuels common in the US

Abstract. A comprehensive suite of instruments was used to quantify the emissions of over 200 organic gases, including methane and volatile organic compounds (VOCs), and 9 inorganic gases from 56 laboratory burns of 18 different biomass fuel types common in the southeastern, southwestern, or northern US. A gas chromatograph-mass spectrometry (GC-MS) instrument provided extensive chemical detail of discrete air samples collected during a laboratory burn and was complemented by real-time measurements of organic and inorganic species via an open-path Fourier transform infrared spectroscopy (OP-FTIR) instrument and three different chemical ionization-mass spectrometers. These measurements were conducted in February 2009 at the US Department of Agriculture's Fire Sciences Laboratory in Missoula, Montana and were used as the basis for a number of emission factors reported by Yokelson et al. (2013). The relative magnitude and composition of the gases emitted varied by individual fuel type and, more broadly, by the three geographic fuel regions being simulated. Discrete emission ratios relative to carbon monoxide (CO) were used to characterize the composition of gases emitted by mass; reactivity with the hydroxyl radical, OH; and potential secondary organic aerosol (SOA) precursors for the 3 different US fuel regions presented here. VOCs contributed less than 0.78 % ± 0.12 % of emissions by mole and less than 0.95 % × 0.07 % of emissions by mass (on average) due to the predominance of CO2, CO, CH4, and NOx emissions; however, VOCs contributed 70–90 (±16) % to OH reactivity and were the only measured gas-phase source of SOA precursors from combustion of biomass. Over 82 % of the VOC emissions by mole were unsaturated compounds including highly reactive alkenes and aromatics and photolabile oxygenated VOCs (OVOCs) such as formaldehyde. OVOCs contributed 57–68 % of the VOC mass emitted, 41–54 % of VOC-OH reactivity, and aromatic-OVOCs such as benzenediols, phenols, and benzaldehyde were the dominant potential SOA precursors. In addition, ambient air measurements of emissions from the Fourmile Canyon Fire that affected Boulder, Colorado in September 2010 allowed us to investigate biomass burning (BB) emissions in the presence of other VOC sources (i.e., urban and biogenic emissions) and identify several promising BB markers including benzofuran, 2-furaldehyde, 2-methylfuran, furan, and benzonitrile.

ACTRIS non-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networks

Abstract. The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5 % and a repeatability of better than 2 % for NMHC mole fractions above 0.1 nmol mol−1. The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N2) at approximately 1 nmol mol−1 and a whole air sample (NMHC_air), following a standardised operation procedure including zero- and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography–flame ionisation detection (GC-FID) or by gas chromatography–mass spectrometry (GC-MS). For the NMHC_N2 measurements, 62 % of the reported values were within the 5 % deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50 % of the reported values within the 5 % deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N2 were a more complex matrix and a larger span of NMHC mole fractions (0.03–2.5 nmol mol−1). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C2–C3 hydrocarbons in the focussing trap, blank values in zero-gas measurements (especially for those systems using a Nafion® Dryer), adsorptive losses of aromatic compounds, and insufficient chromatographic separation.

Characterization of air manganese exposure estimates for residents in two Ohio towns

This study was conducted to derive receptor-specific outdoor exposure concentrations of total suspended particulate (TSP) and respirable (dae ≤ 10 µm) air manganese (air-Mn) for East Liverpool and Marietta (Ohio) in the absence of facility emissions data, but where long-term air measurements were available. Our “site-surface area emissions method” used U.S. Environmental Protection Agency’s (EPA) AERMOD (AMS/EPA Regulatory Model) dispersion model and air measurement data to estimate concentrations for residential receptor sites in the two communities. Modeled concentrations were used to create ratios between receptor points and calibrated using measured data from local air monitoring stations. Estimated outdoor air-Mn concentrations were derived for individual study subjects in both towns. The mean estimated long-term air-Mn exposure levels for total suspended particulate were 0.35 μg/m3 (geometric mean [GM]) and 0.88 μg/m3 (arithmetic mean [AM]) in East Liverpool (range: 0.014–6.32 μg/m3) and 0.17 μg/m3 (GM) and 0.21 μg/m3 (AM) in Marietta (range: 0.03–1.61 μg/m3). Modeled results compared well with averaged ambient air measurements from local air monitoring stations. Exposure to respirable Mn particulate matter (PM10; PM <10 μm) was higher in Marietta residents.Implications: Few available studies evaluate long-term health outcomes from inhalational manganese (Mn) exposure in residential populations, due in part to challenges in measuring individual exposures. Local long-term air measurements provide the means to calibrate models used in estimating long-term exposures. Furthermore, this combination of modeling and ambient air sampling can be used to derive receptor-specific exposure estimates even in the absence of source emissions data for use in human health outcome studies.

First continuous measurements of δ&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O-CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; in air with a Fourier transform infrared spectrometer

Abstract. The continuous in situ measurement of δ18O in atmospheric CO2 opens a new door to differentiating between CO2 source and sink components with high temporal resolution. Continuous 13C–CO2 measurement systems have already been commercially available for some time, but until now, only few instruments have been able to provide a continuous measurement of the oxygen isotope ratio in CO2. Besides precise 13C/12C observations, the Fourier transform infrared (FTIR) spectrometer is also able to measure the 18O / 16O ratio in CO2, but the precision and accuracy of the measurements have not yet been evaluated. Here we present a first analysis of δ18O-CO2 (and δ13C-CO2) measurements with the FTIR analyser in Heidelberg. We used Allan deviation to determine the repeatability of δ18O-CO2 measurements and found that it decreases from 0.25‰ for 10 min averages to about 0.1‰ after 2 h and remains at that value up to 24 h. We evaluated the measurement precision over a 10-month period (intermediate measurement precision) using daily working gas measurements and found that our spectrometer measured δ18O-CO2 to better than 0.3‰ at a temporal resolution of less than 10 min. The compatibility of our FTIR-spectrometric measurements to isotope-ratio mass-spectrometric (IRMS) measurements was determined by comparing FTIR measurements of cylinder gases and ambient air with IRMS measurements of flask samples, filled with gases of the same cylinders or collected from the same ambient air intake. Two-sample t tests revealed that, at the 0.01 significance level, the FTIR and the IRMS measurements do not differ significantly from each other and are thus compatible. We describe two weekly episodes of ambient air measurements, one in winter and one in summer, and discuss what potential insights and new challenges combined highly resolved CO2, δ13C-CO2 and δ18O-CO2 records may provide in terms of better understanding regional scale continental carbon exchange processes.

Influence of temperature and humidity on the strength of low temperature co-fired ceramics

Strength degradation in glass and ceramic materials is related to subcritical crack growth mechanisms acting at the crack tip during mechanical loading. In this work the effect of humidity and temperature on the strength of a commercial low temperature co-fired ceramic was investigated using a biaxial testing procedure. Experiments were performed in argon and in air at different stress rates between 25 and 125°C. The effect of humidity on strength was assessed at room temperature varying only the relative humidity. The sole effect of temperature was evaluated in argon at high stress rates. The combined effect of humidity and temperature was determined in air, testing at different temperatures. Results showed the existence of an inert strength of the material at room temperature. Measurements in ambient air showed a counterbalance effect of temperature and humidity yielding an almost constant strength for this material between 25 and 125°C.

An update to the ambient ratio method for 1-h NO2 air quality standards dispersion modeling

Nitrogen oxide (NOX) gases are typically emitted by fuel combustion sources in the form of nitric oxide (NO), which then reacts with ozone and other oxidants in the atmosphere to convert a portion of the NO to nitrogen dioxide (NO2). EPA has promulgated a 1-h average National Ambient Air Quality Standard (NAAQS) for NO2, and major sources of NOX emissions must estimate their NO2 air quality impacts as part of EPA's air quality permitting programs. The AERMOD dispersion model has been developed by EPA for these air quality impact analyses, and AERMOD contains three different NO to NO2 conversion methods for estimating the ambient concentrations of NO2. This paper describes a refinement to one of the methods, the Ambient Ratio Method version 2 (ARM2). ARM2 is an empirical approach that uses a variable conversion factor, based on an analysis of ambient air measurements of NO and NO2, to estimate the portion of the AERMOD predicted air concentration of total NOX species that is in the form of NO2. The performance of ARM2 has been evaluated and found to compare well to actual ambient measurements and to other more complex EPA conversion methods. EPA has included ARM2 as a “beta-testing” option in AERMOD version 14134, and provided guidance on the use of ARM2 for regulatory modeling analyses in a September 2014 memorandum. This paper also discusses this recent EPA guidance.

High Relative Humidity as a Trigger for Widespread Release of Ice Nuclei

Copyright 2014 American Association for Aerosol Research

A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy

Abstract. The peroxycarboxylic nitric anhydrides (PANs, molecular formula: RC(O)O2NO2) can readily be observed by gas chromatography (PAN-GC) coupled to electron capture detection. Calibration of a PAN-GC remains a challenge, because the response factors differ for each of the PANs, and because their synthesis in sufficiently high purity is non-trivial, in particular for PANs containing unsaturated side chains. In this manuscript, a PAN-GC and its calibration using diffusion standards, whose output was quantified by blue diode laser thermal dissociation cavity ring-down spectroscopy (TD-CRDS), are described. The PAN-GC peak areas correlated linearly with total peroxy nitrate (ΣPN) mixing ratios measured by TD-CRDS (r &gt; 0.96). Accurate determination of response factors required the concentrations of PAN impurities in the synthetic standards to be subtracted from ΣPN. The PAN-GC and its TD-CRDS calibration method were deployed during ambient air measurement campaigns in Abbotsford, BC, from 20 July to 5 August 2012, and during the Fort McMurray Oil Sands Strategic Investigation of Local Sources (FOSSILS) campaign at the AMS13 ground site in Fort McKay, AB, from 10 August to 5 September 2013. The PAN-GC limits of detection for PAN, PPN, and MPAN during FOSSILS were 1, 2, and 3 pptv, respectively. For the Abbotsford data set, the PAN-GC mixing ratios were compared, and agreed with those determined in parallel by thermal dissociation chemical ionization mass spectrometry (TD-CIMS). Advantages and disadvantages of the PAN measurement techniques used in this work and the utility of TD-CRDS as a PAN-GC calibration method are discussed.

Air quality status and trends in Europe

This paper presents an overview and analysis of air quality in Europe from 2002 to 2011. It reviews progress towards meeting the requirements of the EU air quality directives, as well as the development of European air pollutant emissions over the last decade. An overview of the latest findings and estimates of the exposure of urban population and ecosystems to air pollution in Europe is also given. The evaluation of the status and trends of air quality is based on ambient air measurements, in conjunction with data on anthropogenic emissions and their trends. The analysis covers up to 38 European countries, including EU Member States and member countries of the European Environment Agency (EEA) as of 2011.

Comparison of negative-ion proton-transfer with iodide ion chemical ionization mass spectrometry for quantification of isocyanic acid in ambient air

Isocyanic acid (HNCO) is a trace gas pollutant of potential importance to human health whose measurement has recently become possible through the development of negative-ion proton-transfer chemical ionization mass spectrometry (NI-PT-CIMS) with acetate reagent ion. In this manuscript, an alternative ionization and detection scheme, in which HNCO is quantified by iodide CIMS (iCIMS) as a cluster ion at m/z 170, is described. The sensitivity was inversely proportional to water vapor concentration but could be made independent of humidity changes in the sampled air by humidifying the ion–molecule reaction (IMR) region of the CIMS. The performance of the two ionization schemes was compared and contrasted using ambient air measurements of HNCO mixing ratios in Calgary, AB, Canada, by NI-PT-CIMS with acetate reagent ion from Dec 16 to 20, 2013, and by the same CIMS operated in iCIMS mode from Feb 3 to 7, 2014. The iCIMS exhibited a greater signal-to-noise ratio than the NI-PT-CIMS, not because of its sensitivity, which was lower (∼0.083 normalized counts per second (NCPS) per parts-per-trillion by volume (pptv) compared to ∼9.7 NCPS pptv−1), but because of a much lower and more stable background (3 ± 4 compared to a range of ∼2 × 103 to ∼6 × 103 NCPS). For the Feb 2014 data set, the HNCO mixing ratios in Calgary air ranged from <12 to 94 pptv (median 34 pptv), were marginally higher at night than during day, and correlated with nitrogen oxide (NOx = NO + NO2) mixing ratios and submicron particle volume. The ratios of HNCO to NOx observed are within the range of emission ratios reported for gasoline-powered motor vehicles.

Size distribution and chemical composition of particulate matter stack emissions in and around a copper smelter

This paper reports on results from a multi-sampling campaign (stack, fugitive emissions and ambient air measurements) to characterise the geochemical signature of metal and metalloid particles emitted from one of the largest Cu-smelters in the world (in Huelva, SW Spain). Exceptionally high concentrations of very fine particles (<0.33 μm) bearing As, Cd, Pb, Cu, Bi, Zn (∑>100 μg m−3) are emitted from the Flash Smelting Furnaces, but high levels are also emitted by the other main chimney stacks, namely Refining Furnaces, Sulphuric Plant, Converters Unit, and Crushing Plant. Enhanced concentrations of the same elements are also observed in ground measurements near the industrial complex. During the sampling campaign, the presence of plumes from the Cu-smelter over the nearby city of Huelva was identified based on increased concentrations of gaseous pollutants, particulate metals and ultrafine particle numbers (PN). The results demonstrate that the Cu-smelter is an important source of inhalable toxic elements carried by fine airborne particles. The pollution abatement systems applied so far appear to be relatively ineffective in preventing metalliferous air pollution events, potentially increasing health risks to local and regional populations.

Comparisons of continuous atmospheric CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt;, CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O measurements – results from a travelling instrument campaign at Mace Head

Abstract. A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH4 and N2O as well as a cavity ring-down spectroscopy (CRDS) system for CH4 and CO2. The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were −0.04 nmol mol−1 for CH4 and −0.37 nmol mol−1 for N2O (GC-TCI). For N2O, a similar difference (−0.40 nmol mol−1) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMO N2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol−1 for CH4 and 0.14 μmol mol−1 for CO2 (CRDS G1301 – TCI). The difference between both instruments for CO2 could not be explained, as direct measurements of calibration gases show no such difference. The CH4 differences between the TCI, the GC and the CRDS G1301 at Mace Head are much smaller than the WMO inter-laboratory compatibility target, while this is not the case for CO2 and N2O.

Development and Verification of Air Balance Gas Primary Standards for the Measurement of Nitrous Oxide at Atmospheric Levels

The Gas Metrology Group at the National Institute of Standards and Technology (NIST) became active in developing primary standards at ambient levels of N2O in the 1980s, and this has continued through to the present. In recent years, interest in NIST-traceable standards has increased-not only at the ambient level of approximately 325 nmol mol(-1) (ppb) but at micromole per mole (ppm) levels as well. In order to support two in-process dry whole air standard reference materials (SRMs 1720 and 1721) and the NIST Traceable Reference Materials (NTRM) program, a project was implemented in the Gas Metrology Group to produce a complete suite of new primary standard materials (PSMs) of N2O with synthetic air (O2/N2) as the balance gas. Six levels of dilution, approximately 1 order of magnitude apart, were gravimetrically prepared and verified. Each level serves as the "parent mix" for the next level. This discussion describes the process of producing each level and then verifying its amount-of-substance fraction. Expanded uncertainties, k = 2, of 0.025% relative to the gravimetric amount-of-substance fraction were obtained at the ambient level. One standard from the final group of standards at the ambient amount-of-substance fraction level was compared with standards from the National Oceanographic and Atmospheric Administration and the Scripps Institution of Oceanography, two organizations experienced in gas standards preparation and ambient whole air measurements, and shows agreement to 0.07 nmol mol(-1) (0.02% relative) and 0.20 nmol mol(-1) (0.06% relative), respectively.

Assessment of source-specific health effects associated with an unknown number of major sources of multiple air pollutants: a unified Bayesian approach

There has been increasing interest in assessing health effects associated with multiple air pollutants emitted by specific sources. A major difficulty with achieving this goal is that the pollution source profiles are unknown and source-specific exposures cannot be measured directly; rather, they need to be estimated by decomposing ambient measurements of multiple air pollutants. This estimation process, called multivariate receptor modeling, is challenging because of the unknown number of sources and unknown identifiability conditions (model uncertainty). The uncertainty in source-specific exposures (source contributions) as well as uncertainty in the number of major pollution sources and identifiability conditions have been largely ignored in previous studies. A multipollutant approach that can deal with model uncertainty in multivariate receptor models while simultaneously accounting for parameter uncertainty in estimated source-specific exposures in assessment of source-specific health effects is presented in this paper. The methods are applied to daily ambient air measurements of the chemical composition of fine particulate matter ([Formula: see text]), weather data, and counts of cardiovascular deaths from 1995 to 1997 for Phoenix, AZ, USA. Our approach for evaluating source-specific health effects yields not only estimates of source contributions along with their uncertainties and associated health effects estimates but also estimates of model uncertainty (posterior model probabilities) that have been ignored in previous studies. The results from our methods agreed in general with those from the previously conducted workshop/studies on the source apportionment of PM health effects in terms of number of major contributing sources, estimated source profiles, and contributions. However, some of the adverse source-specific health effects identified in the previous studies were not statistically significant in our analysis, which probably resulted because we incorporated parameter uncertainty in estimated source contributions that has been ignored in the previous studies into the estimation of health effects parameters.

Investigation of time-resolved atmospheric conditions and indoor/outdoor particulate matter concentrations in homes with gas and biomass cook stoves in Nogales, Sonora, Mexico

This paper reports findings from a case study designed to investigate indoor and outdoor air quality in homes near the United States–Mexico border. During the field study, size-resolved continuous particulate matter (PM) concentrations were measured in six homes, while outdoor PM was simultaneously monitored at the same location in Nogales, Sonora, Mexico, during March 14–30, 2009. The purpose of the experiment was to compare PM in homes using different fuels for cooking, gas versus biomass, and to obtain a spatial distribution of outdoor PM in a region where local sources vary significantly (e.g., highway, border crossing, unpaved roads, industry). Continuous PM data were collected every 6 seconds using a valve switching system to sample indoor and outdoor air at each home location. This paper presents the indoor PM data from each home, including the relationship between indoor and outdoor PM. The meteorological conditions associated with elevated ambient PM events in the region are also discussed. Results indicate that indoor air pollution has a strong dependence on cooking fuel, with gas stoves having hourly averaged median PM3 concentrations in the range of 134 to 157 μg m−3 and biomass stoves 163 to 504 μg m−3. Outdoor PM also indicates a large spatial heterogeneity due to the presence of microscale sources and meteorological influences (median PM3: 130 to 770 μg m−3). The former is evident in the median and range of daytime PM values (median PM3: 250 μg m−3, maximum: 9411 μg m−3), while the meteorological influences appear to be dominant during nighttime periods (median PM3: 251 μg m−3, maximum: 10,846 μg m−3). The atmospheric stability is quantified for three nighttime temperature inversion episodes, which were associated with an order of magnitude increase in PM10 at the regulatory monitor in Nogales, AZ (maximum increase: 12 to 474 μg m−3).Implications:Regulatory air quality standards are based on outdoor ambient air measurements. However, a large fraction of time is typically spent indoors where a variety of activities including cooking, heating, tobacco smoking, and cleaning can lead to elevated PM concentrations. This study investigates the influence of meteorology, outdoor PM, and indoor activities on indoor air pollution (IAP) levels in the United States–Mexico border region. Results indicate that cooking fuel type and meteorology greatly influence the IAP in homes, with biomass fuel use causing the largest increase in PM concentration.

Influence of air diffusion on the OH radicals and atomic O distribution in an atmospheric Ar (bio)plasma jet

Treatment of samples with plasmas in biomedical applications often occurs in ambient air. Admixing air into the discharge region may severely affect the formation and destruction of the generated oxidative species. Little is known about the effects of air diffusion on the spatial distribution of OH radicals and O atoms in the afterglow of atmospheric-pressure plasma jets. In our work, these effects are investigated by performing and comparing measurements in ambient air with measurements in a controlled argon atmosphere without the admixture of air, for an argon plasma jet. The spatial distribution of OH is detected by means of laser-induced fluorescence diagnostics (LIF), whereas two-photon laser-induced fluorescence (TALIF) is used for the detection of atomic O. The spatially resolved OH LIF and O TALIF show that, due to the air admixture effects, the reactive species are only concentrated in the vicinity of the central streamline of the afterglow of the jet, with a characteristic discharge diameter of ∼1.5 mm. It is shown that air diffusion has a key role in the recombination loss mechanisms of OH radicals and atomic O especially in the far afterglow region, starting up to ∼4 mm from the nozzle outlet at a low water/oxygen concentration. Furthermore, air diffusion enhances OH and O production in the core of the plasma. The higher density of active species in the discharge in ambient air is likely due to a higher electron density and a more effective electron impact dissociation of H2O and O2 caused by the increasing electrical field, when the discharge is operated in ambient air.

Total OH reactivity measurements in ambient air in a southern Rocky mountain ponderosa pine forest during BEACHON-SRM08 summer campaign

Total OH reactivity was measured during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen-Southern Rocky Mountain 2008 field campaign (BEACHON-SRM08) held at Manitou Experimental Forest (MEF) in Colorado USA in August, 2008. The averaged total OH reactivity was 6.7 s−1, smaller than that measured in urban (33.4 s−1, Yoshino et al., 2012) and suburban (27.7 s−1, Yoshino et al., 2006) areas in Tokyo in the same season, while sporadically high OH reactivity was also observed during some evenings. The total OH reactivity measurements were accompanied by observations of traces species such as CO, NO, NOy, O3 and SO2 and Volatile Organic Compounds (VOCs). From the calculation of OH reactivity based on the analysis of these trace species, 46.3% of OH reactivity for VOCs came from biogenic species that are dominated by 2-methyl-3-buten-2-ol (MBO), and monoterpenes. MBO was the most prominent contribution to OH reactivity of all trace species. A comparison of observed and calculated OH reactivity shows that the calculated OH reactivity is 29.5% less than the observed value, implying the existence of missing OH sinks. One of the candidates of missing OH is thought to be the oxidation products of biogenic species.

Attribution of primary formaldehyde and sulfur dioxide at Texas City during SHARP/formaldehyde and olefins from large industrial releases (FLAIR) using an adjoint chemistry transport model

AbstractAn adjoint version of the Houston Advanced Research Center (HARC) neighborhood air quality model with 200 m horizontal resolution, coupled offline to the Quick Urban &amp; Industrial Complex (QUIC‐URB) fast response urban wind model, was used to perform 4‐D variational (4Dvar) inverse modeling of an industrial release of formaldehyde (HCHO) and sulfur dioxide (SO2) in Texas City, Texas during the 2009 Study of Houston Atmospheric Radical Precursors (SHARP). The source attribution was based on real‐time observations by the Aerodyne mobile laboratory and a high resolution 3‐D digital model of the emitting petrochemical complex and surrounding urban canopy. The inverse model estimate of total primary HCHO emitted during the incident agrees very closely with independent remote sensing estimates based on both Imaging and Multi‐Axis Differential Optical Absorption Spectroscopy (DOAS). Whereas a previous analysis of Imaging DOAS data attributed the HCHO release to a Fluidized Catalytic Cracking Unit (FCCU), the HARC model attributed most of the HCHO event emissions to both the FCCU and desulfurization processes. Fugitives contributed significantly to primary HCHO, as did combustion processes, whereas the latter accounted for most SO2 event emissions. The inferred HCHO‐to‐SO2 molar emission ratio was similar to that computed directly from ambient air measurements during the release. The model‐estimated HCHO‐to‐CO molar emission ratio for combustion units with significant inferred emissions ranged from 2% to somewhat less than 7%, consistent with other observationally‐based estimates obtained during SHARP. A model sensitivity study demonstrated that the inclusion of urban morphology has a significant, but not critical, impact on the source attribution.

Validation Test for CAP88 Predictions of Tritium Dispersion at Los Alamos National Laboratory

Gaussian plume models, such as CAP88, are used regularly for estimating downwind concentrations from stack emissions. At many facilities, the U.S. Environmental Protection Agency (U.S. EPA) requires that CAP88 be used to demonstrate compliance with air quality regulations for public protection from emissions of radionuclides. Gaussian plume models have the advantage of being relatively simple and their use pragmatic; however, these models are based on simplifying assumptions and generally they are not capable of incorporating dynamic meteorological conditions or complex topography. These limitations encourage validation tests to understand the capabilities and limitations of the model for the specific application. Los Alamos National Laboratory (LANL) has complex topography but is required to use CAP88 for compliance with the Clean Air Act Subpart H. The purpose of this study was to test the accuracy of the CAP88 predictions against ambient air measurements using released tritium as a tracer. Stack emissions of tritium from two LANL stacks were measured and the dispersion modeled with CAP88 using local meteorology. Ambient air measurements of tritium were made at various distances and directions from the stacks. Model predictions and ambient air measurements were compared over the course of a full year's data. Comparative results were consistent with other studies and showed the CAP88 predictions of downwind tritium concentrations were on average about three times higher than those measured, and the accuracy of the model predictions were generally more consistent for annual averages than for bi-weekly data.