A nocturnal atmospheric loss of CH2I2 in the remote marine boundary layer.

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH2I2) and chloro-iodomethane (CH2ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH2I2 and CH2ICl in air and of CH2I2 in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH2I2 was lower in amplitude than that of CH2ICl, despite its faster photolysis rate. We speculate that night-time loss of CH2I2 occurs due to reaction with NO3 radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k CH2I2+NO3 of ≤4 × 10-13 cm3 molecule-1 s-1; a previous kinetic study carried out at ≤100 Torr found k CH2I2+NO3 of 4 × 10-13 cm3 molecule-1 s-1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/- 0.8 nmol m-2 d-1 for CH2I2 and 3.7 +/- 0.8 nmol m-2 d-1 for CH2ICl), we show that the model overestimates night-time CH2I2 by >60 % but reaches good agreement with the measurements when the CH2I2 + NO3 reaction is included at 2-4 × 10-13 cm3 molecule-1 s-1. We conclude that the reaction has a significant effect on CH2I2 and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.LJC acknowledges NERC (NE/J00619X/1) and the National Centre for Atmospheric Science (NCAS) for funding. The laboratory work was supported by the NERC React-SCI (NE/K005448/1) and RONOCO (NE/F005466/1) grants.This is the final version of the article. It was first available from Springer via http://dx.doi.org/10.1007/s10874-015-9320-

The state of ambient air quality in Pakistan—a review

Background and purpose: Pakistan, during the last decade, has seen an extensive escalation in population growth, urbanization, and industrialization, together with a great increase in motorization and energy use. As a result, a substantial rise has taken place in the types and number of emission sources of various air pollutants. However, due to the lack of air quality management capabilities, the country is suffering from deterioration of air quality. Evidence from various governmental organizations and international bodies has indicated that air pollution is a significant risk to the environment, quality of life, and health of the population. The Government has taken positive steps toward air quality management in the form of the Pakistan Clean Air Program and has recently established a small number of continuous monitoring stations. However, ambient air quality standards have not yet been established. This paper reviews the data being available on the criteria air pollutants: particulate matter (PM), sulfur dioxide, ozone, carbon monoxide, nitrogen dioxide, and lead. Methods: Air pollution studies in Pakistan published in both scientific journals and by the Government have been reviewed and the reported concentrations of PM, SO2, O3, CO, NO2, and Pb collated. A comparison of the levels of these air pollutants with the World Health Organization air quality guidelines was carried out. Results: Particulate matter was the most serious air pollutant in the country. NO2 has emerged as the second high-risk pollutant. The reported levels of PM, SO2, CO, NO2, and Pb were many times higher than the World Health Organization air quality guidelines. Only O3 concentrations were below the guidelines. Conclusions: The current state of air quality calls for immediate action to tackle the poor air quality. The establishment of ambient air quality standards, an extension of the continuous monitoring sites, and the development of emission control strategies are essential. © Springer-Verlag 2009

UV absorption cross-sections and atmospheric photolysis lifetimes of halogenated aldehydes

UV absorption cross-sections for CCl3CHO, CCl2FCHO and CCIF2CHO have been determined over the wavelength range 200-370 nm and at temperatures in the range 298-243 K using a dual beam diode array spectrometer. The spectra show characteristic absorption due to the n --> pi* transition of the C=O group with absorption maxima around 300 nm. On substitution of Cl by F in the CX3 group the absorption maxima showed a shift to longer wavelengths and a corresponding increase in the intensity of the absorption in the region of atmospheric photolysis. With decreasing temperature, all three aldehydes showed a small non-negligible decrease in the cross-section in the long wavelength tail of the absorption band, and an increase in the cross-section around the absorption maxima. A two-dimensional photochemical model has been used to calculate atmospheric lifetimes due to photodissociation and OH radical loss. (C) 1998 Elsevier Science S.A

Temperature-dependent absorption cross-sections of CF3COCl, CF3COF, CH3COF, CCl3CHO and CF3COOH

Absorption cross-sections for CF3COCl, CF3COF, CH3COF, CCl3CHO and CFCOOH have been measured in the wavelength region 200-360 nm, using a dual-beam diode-array spectrometer, with a spectral resolution (FWHM) of 1.2 nm. The temperature dependence of the absorption cross-sections was investigated for CF3COCl, CF3COF and CCl3CHO. Absorption over most of the wavelength range showed a distinct temperature dependence, with a significant decline in the cross-section in the long wavelength tail with decreasing temperature. The calculated atmospheric photolysis lifetimes suggest that in the troposphere, photolysis is an important removal process for both CF3COCl and CC13CHO but is unimportant for CF3COF, CF3COOH and CH3COF

Mechanism of atmospheric oxidation of 1,1,1,2-tetrafluoroethane (HFC 134a)

The chlorine-initiated photooxidation of hydrofluorocarbon 134a (CF3CH2F) has been studied in the temperature range 235-318 K and at 1 atm total pressure using UV absorption. Trifluoroacetyl fluoride [CF3C(O)F] and formyl fluoride [HC(O)F] were observed as the major products. IR analysis of the reaction mixture also showed carbonyl fluoride [C(O)F2] as a product. By measurement of the yields of HC(O)F from the photooxidation as a function of [O2] and temperature, the rate of the unimolecular decomposition of the oxy radical, CF3CHFO, reaction (5), was determined relative to its reaction with O2, reaction (4): CF3CHFO + O2 --> CF3C(O)F + HO2 (4) CF3CHFO --> CF3 + HO(O))F (5). The results were treated using both an arithmetic derivation and numerical integration with a detailed reaction scheme. Inclusion of other recently published kinetic data leads to the following recommended rate expression for reaction (5) at 1 atm k5 = 7.4 x 10(11) exp[(-4720 +/- 220)/T] s-1. The errors are 1sigma. The observation of enhanced product yields in the present work is attributed to the reaction of the CF3O radical with HFC 134a leading to further peroxy radical formation. The results have been incorporated into a 2D atmospheric model to assess the environmental implications of HFC 134a release in the troposphere

Source apportionment of PM 2.5 chemically speciated mass and particle number concentrations in New York City

The major sources of fine particulate matter (PM2.5) in New York City (NYC) were apportioned by applying positive matrix factorization (PMF) to two different sets of particle characteristics: mass concentrations using chemical speciation data and particle number concentrations (PNC) using number size distribution, continuously monitored gases, and PM2.5 data. Post-processing was applied to the PMF results to: (i) match with meteorological data, (ii) use wind data to detect the likely locations of the local sources, and (iii) use concentration weighted trajectory models to assess the strength of potential regional/transboundary sources. Nine sources of PM2.5 mass were apportioned and identified as: secondary ammonium sulfate, secondary ammonium nitrate, road traffic exhaust, crustal dust, fresh sea-salt, aged sea-salt, biomass burning, residual oil/domestic heating and zinc. The sources of PNC were investigated using hourly average number concentrations in six size bins, gaseous air pollutants, mass concentrations of PM2.5, particulate sulfate, OC, and EC. These data were divided into 3 periods indicative of different seasonal conditions. Five sources were resolved for each period: secondary particles, road traffic, NYC background pollution (traffic and oil heating largely in Manhattan), nucleation and O3-rich aerosol. Although traffic does not account for large amounts of PM2.5 mass, it was the main source of particles advected from heavily trafficked zones. The use of residual oil had limited impacts on PM2.5 mass but dominates PNC in cold periods

Analysis of major air pollutants and submicron particles in New York City and Long Island

A year-long sampling campaign of major air pollutants and submicron particle number size distributions was conducted at two sites taken as representative of city-wide air quality in New York City and Long Island, respectively. A number of species were quantified with hourly time resolution, including particle number concentrations in 6 size ranges (20-30 nm, 30-50 nm, 50-70 nm, 70-100 nm, 100-200 nm, and >200 nm), nitrogen oxides, sulfur dioxide, ozone, carbon monoxide, methane, non-methane hydrocarbons, PM2.5 mass concentration and some PM major components (sulfate, organic and elemental carbon). Hourly concentrations of primary and secondary organic carbon were estimated using the EC tracer method. Data were matched with weather parameters and air parcel back-trajectories. A series of tools were thus applied to: (i) study the seasonal, weekly, diurnal cycles of pollutants; (ii) investigate the relationships amongst pollutants through correlation and lagged correlation analyses; (iii) depict the role of atmospheric photochemical processes; (iv) examine the location of the potential sources by mean of conditional bivariate probability function analysis and (v) investigate the role of regional transport of air masses to the concentrations of analyzed species. Results indicate that concentrations of NOx, SO2, CO, non-methane hydrocarbons, primary OC and EC are predominantly determined by local sources, but are also affected by regional transports of polluted air masses. On the contrary, the transport of continental polluted air masses has a main effect in raising the concentrations of secondary PM2.5 (sulfate and secondary organic carbon). By providing direct information on the concentrations and trends of key pollutants and submicron particle number concentrations, this study finally enables some general considerations about air quality status and atmospheric processes over the New York City metropolitan area. (C) 2016 Elsevier Ltd. All rights reserved