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Photochemical pollution control strategies require an understanding of photochemical oxidation precursors, making it important to distinguish between primary and secondary sources of HCHO. Estimates for the relative strengths of primary and secondary sources of formaldehyde (HCHO) were obtained using a statistical regression analysis with time series data of carbon monoxide (CO) and glyoxal (CHOCHO) measured in the Mexico City Metropolitan Area (MCMA) during the spring of 2003. Differences between Easter week and more typical weeks are evaluated. The use of CO-CHOCHO as HCHO tracers is more suitable for differentiating primary and secondary sources than CO-O<sub>3</sub>. The application of the CO-O<sub>3</sub> tracer pair to mobile laboratory data suggests a potential in-city source of background HCHO. A significant amount of HCHO observed in the MCMA is associated with primary emissions.
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Iodotrifluoromethane (CF<sub>3</sub>I) has been considered to be a candidate replacement for bromotrifluoromethane (CF<sub>3</sub>Br), which is used in aircraft for fuel inerting and for fire fighting. In this study, the chemical effects of aircraft-released CF<sub>3</sub>I on atmospheric ozone were examined with the University of Illinois at Urbana-Champaign two-dimensional chemical-radiative-transport (UIUC 2-D CRT) model. Using an earlier estimate of the aircraft emission profile for tank inerting in military aircraft, the resulting equivalent Ozone Depletion Potentials (ODPs) for CF<sub>3</sub>I were in the range of 0.07 to 0.25. As a sensitivity study, we also analyzed CF<sub>3</sub>I emissions associated with fuel inerting if it were to occur at lower altitudes using an alternative estimate. The model calculations of resulting effects on ozone for this case gave ODPs≤0.05. Furthermore, through interactions with the National Institute of Standards and Technology (NIST), we analyzed the potential effects on ozone resulting from using CF<sub>3</sub>I in fire fighting connected with engine nacelle and auxiliary power unit applications. The scenarios evaluated using the NIST estimate suggested that the ODPs obtained by assuming aircraft flights occurring in several different latitude regions of the Northern Hemisphere are extremely low. According to the model calculation, the altitude where CF<sub>3</sub>I is released from aircraft is a dominant factor in its ozone depletion effects. On the assumption that the CF<sub>3</sub>I emission profile is representative of actual release characteristics, aircraft-released CF<sub>3</sub>I has much lower impacts than CF<sub>3</sub>Br.
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Aerosols play an important role in the atmosphere but are poorly characterized, particularly in urban areas like the Mexico City Metropolitan Area (MCMA). The chemical composition of urban particles must be known to assess their effects on the environment, and specific particulate emissions sources should be identified to establish effective pollution control standards. For these reasons, samples of particulate matter ≤2.5 μm (PM<sub>2.5</sub>) were collected during the MCMA-2003 Field Campaign for elemental and multivariate analyses. Proton-Induced X-ray Emission (PIXE), Proton-Elastic Scattering Analysis (PESA) and Scanning Transmission Ion Microscopy (STIM) measurements were done to determine concentrations of 19 elements from Na to Pb, hydrogen, and total mass, respectively. The most abundant elements from PIXE analysis were S, Si, K, Fe, Ca, and Al, while the major emissions sources associated with these elements were industry, wind-blown soil, and biomass burning. Wind trajectories suggest that metals associated with industrial emissions came from northern areas of the city whereas soil aerosols came from the southwest and increased in concentration during dry conditions. Elemental markers for fuel oil combustion, V and Ni, correlated with a large SO<sub>2</sub> plume to suggest an anthropogenic, rather than volcanic, emissions source. By subtracting major components of soil and sulfates determined by PIXE analysis from STIM total mass measurements, we estimate that approximately 50% of non-volatile PM<sub>2.5</sub> consisted of carbonaceous material.
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We present the submodels DRYDEP and SEDI for the Modular Earth Submodel System (MESSy). Dry deposition of gases and aerosols is calculated within DRYDEP, whereas SEDI deals with aerosol particle sedimentation. Dry deposition velocities depend on the near-surface turbulence and the physical and chemical properties of the surface cover (e.g. the roughness length, soil pH or leaf stomatal exchange). The dry deposition algorithm used in DRYDEP is based on the big leaf approach and is described in detail within this Technical Note. The sedimentation submodel SEDI contains two sedimentation schemes: a simple upwind zeroth order scheme and a first order approach.
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To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM<sub>2.5</sub> and PM<sub>10</sub> samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ<sup>13</sup>C) of OC and EC were –26.9±0.5‰ and –25.6±0.1‰, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC <sup>13</sup>C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.
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An airborne instrument that measures altitude temperature profiles is ideally suited for the task of characterizing statistical properties of the vertical displacement of isentrope surfaces. Prior measurements of temperature fluctuations during level flight could not be used to infer isentrope altitude variations because lapse rate information was missing. The Microwave Temperature Profiler instrument, which includes lapse rate measurements at flight level as a part of temperature profiles, has been used on hundreds of flights to produce altitude versus ground track cross-sections of potential temperature. These cross-sections show isentrope altitude variations with a horizontal resolution of ~3 km for a >6 km altitude region. An airborne isentrope-altitude cross-section (IAC) can be compared with a counterpart IAC generated from synoptic scale data, based on radiosondes and satellite instruments, in order to assess differences between the altitudes of isentrope surfaces sampled at mesoscale versus synoptic scale. It has been found that the synoptic scale isentropes fail to capture a significant component of vertical displacement of isentrope surfaces, especially in the vicinity of jet streams. Under the assumptions that air parcels flow along isentrope surfaces, and change temperature adiabatically while undergoing altitude displacements, it is possible to compute mesoscale temperature fluctuations that are not present in synoptic scale back trajectory parcel temperature histories. It has been found that the magnitude of the mesoscale component of temperature fluctuations varies with altitude, season, latitude and underlying topography. A model for these dependences is presented, which shows, for example, that mesoscale temperature fluctuations increase with altitude in a systematic way, are greatest over mountainous terrain, and are greater at polar latitudes during winter.
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The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263–303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22–0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (<i>K<sub>om,i</sub></i>) and the stoichiometric yields (α<sub><i>i</i></sub>) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.
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Literature reports have differed on the possibilities of discontinuous and continuous (i.e., prompt and nonprompt) deliquescence and efflorescence of aerosol particles in the nanosize regime. Experiments reported herein using a hygroscopic tandem nano-differential mobility analyzer demonstrate prompt deliquescence and efflorescence of ammonium sulfate particles having diameters from 6 to 60 nm. Apparent nonpromptness can be induced both by operation of the experimental apparatus and by interpretation of the measurements, even though the underlying phase transitions of individual particles remain prompt. No nanosize effect on the relative humidity values of deliquescence or efflorescence is observed for the studied size range. Smaller hygroscopic growth factors are, however, observed for the nanoparticles, in agreement with thermodynamic calculations that include the Kelvin effect. A slightly nonspherical shape for dry ammonium sulfate particles is inferred from their hygroscopically induced reconstruction between 5 and 30% relative humidity. Our results provide a further understanding of nanoparticle behavior, especially relevant to the growth rates of atmospheric nanoparticles.
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The most direct approach for measuring the exchange of biogenic volatile organic compounds between terrestrial ecosystems and the atmosphere is the eddy covariance technique. It has been applied several times in the last few years using fast response proton-transfer-reaction mass spectrometry (PTR-MS). We present an independent validation of this technique by applying it to measure the water vapour flux in comparison to a common reference system comprising an infra-red gas analyser (IRGA). Water vapour was detected in the PTR-MS at mass 37 (atomic mass units) corresponding to the cluster ion H<sub>3</sub>O<sup>+</sup>·H<sub>2</sub>O. During a five-week field campaign at a grassland site, we obtained a non-linear but stable calibration function between the mass 37 signal and the reference water vapour concentration. With a correction of the high-frequency damping loss based on empirical ogive analysis, the eddy covariance water vapour flux obtained with the PTR-MS showed a very good agreement with the flux of the reference system. The application of the empirical ogive method for high-frequency correction led to significantly better results than using a correction based on theoretical spectral transfer functions. This finding is attributed to adsorption effects on the tube walls that are presently not included in the theoretical correction approach. The proposed high-frequency correction method can also be used for other trace gases with different adsorption characteristics.
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Tropospheric ozone depletion events (ODEs) at high latitudes were discovered 20 years ago and are attributed to bromine explosions. However, an unresolved issue is the explanation of how the acid-catalyzed reaction cycle is triggered in atmospheric particles derived from alkaline sea water. By simulating the chemistry occuring in polar regions over recently formed sea ice, we can model successfully the transformation of inert sea-salt bromide to reactive bromine monoxide (BrO) and the subsequent ODE when precipitation of calcium carbonate from freezing sea water is taken into account. In addition, we found the temperature dependence of the equilibrium BrCl+Br<sup>−</sup>↔Br<sub>2</sub>Cl<sup>−</sup> to be important.
