Delineation of geological problems for use in urban planning

Activities of the University of Alabama in support of state and local planning commissions are reported. Demonstrations were given of the various types of remotely sensed images available from U-2, Skylab, and LANDSAT; and their uses and limitations were discussed. Techniques to be used in determining flood prone areas were provided for environmental studies. A rapid, inexpensive method for study was developed by which imagery is copied on 35 mm film and projected on existing topographic maps for measuring delta volume and growth

Kinetics of n-Butoxy and 2-Pentoxy Isomerization and Detection of Primary Products by Infrared Cavity Ringdown Spectroscopy

The primary products of n-butoxy and 2-pentoxy isomerization in the presence and absence of O_2 have been detected using pulsed laser photolysis-cavity ringdown spectroscopy (PLP-CRDS). Alkoxy radicals n-butoxy and 2-pentoxy were generated by photolysis of alkyl nitrite precursors (n-butyl nitrite or 2-pentyl nitrite, respectively), and the isomerization products with and without O_2 were detected by infrared cavity ringdown spectroscopy 20 μs after the photolysis. We report the mid-IR OH stretch (ν_1) absorption spectra for δ-HO-1-C_4H_8•, δ-HO-1-C_4H_8OO•, δ-HO-1-C_5H_(10)•, and δ-HO-1-C_5H_(10)OO•. The observed ν_1 bands are similar in position and shape to the related alcohols (n-butanol and 2-pentanol), although the HOROO• absorption is slightly stronger than the HOR• absorption. We determined the rate of isomerization relative to reaction with O_2 for the n-butoxy and 2-pentoxy radicals by measuring the relative ν_1 absorbance of HOROO• as a function of [O_2]. At 295 K and 670 Torr of N_2 or N_2/O_2, we found rate constant ratios of k_(isom)/k_(O2) = 1.7 (±0.1) × 10^(19) cm^(–3) for n-butoxy and k_(isom)/k_(O2) = 3.4(±0.4) × 10^(19) cm^(–3) for 2-pentoxy (2σ uncertainty). Using currently known rate constants k_(O2), we estimate isomerization rates of k_(isom) = 2.4 (±1.2) × 10^5 s^(–1) and k_(isom) ≈ 3 × 10^5 s^(–1) for n-butoxy and 2-pentoxy radicals, respectively, where the uncertainties are primarily due to uncertainties in k_(O2). Because isomerization is predicted to be in the high pressure limit at 670 Torr, these relative rates are expected to be the same at atmospheric pressure. Our results include corrections for prompt isomerization of hot nascent alkoxy radicals as well as reaction with background NO and unimolecular alkoxy decomposition. We estimate prompt isomerization yields under our conditions of 4 ± 2% and 5 ± 2% for n-butoxy and 2-pentoxy formed from photolysis of the alkyl nitrites at 351 nm. Our measured relative rate values are in good agreement with and more precise than previous end-product analysis studies conducted on the n-butoxy and 2-pentoxy systems. We show that reactions typically neglected in the analysis of alkoxy relative kinetics (decomposition, recombination with NO, and prompt isomerization) may need to be included to obtain accurate values of k_(isom)/k_(O2)

Iodine monoxide at a clean marine coastal site: observations of high frequency variations and inhomogeneous distributions

The first in situ point observations of iodine monoxide (IO) at a clean marine site were made using a laser-induced fluorescence instrument deployed at Mace Head, Ireland in August 2007. IO mixing ratios of up to 49.8 pptv (equivalent to pmol mol<sup>−1</sup>; 1 s average) were observed at day-time low tide, well in excess of previous observed spatially-averaged maxima. A strong anti-correlation of IO mixing ratios with tide height was evident and the high time resolution of the observations showed IO peaked in the hour after low tide. The temporal delay in peak IO compared to low tide has not been observed previously but coincides with the time of peak aerosol number previously observed at Mace Head. <br><br> A long path-differential optical absorption spectroscopy instrument (with a 2 × 6.8 km folded path across Roundstone Bay) was also based at the site for 3 days during the point measurement observation period. Both instruments show similar temporal trends but the point measurements of IO are a factor of ~6–10 times greater than the spatially averaged IO mixing ratios, providing direct empirical evidence of the presence of inhomogeneities in the IO mixing ratio near the intertidal region

60 years of UK visibility measurements:Impact of meteorology and atmospheric pollutants on visibility

Reduced visibility is an indicator of poor air quality. Moreover, degradation in visibility can be hazardous to human safety; for example, low visibility can lead to road, rail, sea and air accidents. In this paper, we explore the combined influence of atmospheric aerosol particle and gas characteristics, and meteorology, on long-term visibility. We use visibility data from eight meteorological stations, situated in the UK, which have been running since the 1950s. The site locations include urban, rural and marine environments.<br><br> Most stations show a long-term trend of increasing visibility, which is indicative of reductions in air pollution, especially in urban areas. Additionally, the visibility at all sites shows a very clear dependence on relative humidity, indicating the importance of aerosol hygroscopicity on the ability of aerosol particles to scatter radiation. The dependence of visibility on other meteorological parameters, such as wind speed and wind direction, is also investigated. Most stations show long-term increases in temperature which can be ascribed to climate change, land-use changes (e.g. urban heat island effects) or a combination of both; the observed effect is greatest in urban areas. The impact of this temperature change upon local relative humidity is discussed. <br><br> To explain the long-term visibility trends and their dependence on meteorological conditions, the measured data were fitted to a newly developed light-extinction model to generate predictions of historic aerosol and gas scattering and absorbing properties. In general, an excellent fit was achieved between measured and modelled visibility for all eight sites. The model incorporates parameterizations of aerosol hygroscopicity, particle concentration, particle scattering, and particle and gas absorption. This new model should be applicable and is easily transferrable to other data sets worldwide. Hence, historical visibility data can be used to assess trends in aerosol particle properties. This approach may help constrain global model simulations which attempt to generate aerosol fields for time periods when observational data are scarce or non-existent. Both the measured visibility and the modelled aerosol properties reported in this paper highlight the success of the UK's Clean Air Act, which was passed in 1956, in cleaning the atmosphere of visibility-reducing pollutants.</p

Evidence for renoxification in the tropical marine boundary layer

We present 2 years of NOx observations from the Cape Verde Atmospheric Observatory located in the tropical Atlantic boundary layer. We find that NOx mixing ratios peak around solar noon (at 20-30pptV depending on season), which is counter to box model simulations that show a midday minimum due to OH conversion of NO2 to HNO3. Production of NOx via decomposition of organic nitrogen species and the photolysis of HNO3 appear insufficient to provide the observed noontime maximum. A rapid photolysis of nitrate aerosol to produce HONO and NO2, however, is able to simulate the observed diurnal cycle. This would make it the dominant source of NOx at this remote marine boundary layer site, overturning the previous paradigm according to which the transport of organic nitrogen species, such as PAN, is the dominant source. We show that observed mixing ratios (November-December 2015) of HONO at Cape Verde (∼ 3.5pptV peak at solar noon) are consistent with this route for NOx production. Reactions between the nitrate radical and halogen hydroxides which have been postulated in the literature appear to improve the box model simulation of NOx. This rapid conversion of aerosol phase nitrate to NOx changes our perspective of the NOx cycling chemistry in the tropical marine boundary layer, suggesting a more chemically complex environment than previously thought

Design of and initial results from a highly instrumented reactor for atmospheric chemistry (HIRAC)

International audienceThe design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; and NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and measurements of the blacklamp flux have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response under a range of atmospheric conditions

HONO Measurement by Differential Photolysis

Nitrous acid (HONO) has been quantitatively measured in situ by differential photolysis at 385 and 395 nm, and subsequent detection as nitric oxide (NO) by the chemiluminescence reaction with ozone (O3). The technique has been evaluated by Fourier transform infrared (FT-IR) spectroscopy to provide a direct HONO measurement in a simulation chamber and compared side by side with a long absorption path optical photometer (LOPAP) in the field. The NO-O3 chemiluminescence technique is robust, well characterized, and capable of sampling at low pressure, whilst solid-state converter technology allows for unattended in situ HONO measurements in combination with fast time resolution and response