Release of gaseous bromine from the photolysis of nitrate and hydrogen peroxide in simulated sea-salt solutions

We have carried out a series of laboratory experiments to investigate the oxidation of bromide (Br⁻) by hydroxyl radical (OH) in solutions used to mimic sea-salt particles. Aqueous halide solutions with nitrate or hydrogen peroxide (HOOH) as a photochemical source of OH were illuminated with 313 nm light and the resulting gaseous bromine (Br*(g)) was collected. While illumination of these solutions nearly always formed gaseous bromine (predominantly Br₂ based on modeling results), there was no evidence for the release of gaseous chlorine. The rate of Br*(g) release increased (up to a plateau value) with increasing concentrations of bromide and was enhanced at lower pH values for both nitrate and HOOH solutions. Increased ionic strength in nitrate solutions inhibited Br*(g) release and the extent of inhibition was dependent upon the salt used. In HOOH solutions, however, no ionic strength effects were observed and the presence of Cl⁻ strongly enhanced Br*(g) release.Overall, for conditions typical of aged, deliquesced, sea-salt particles, the efficiencies of gaseous bromine release, expressed as mole of Br*(g) released per mole of OH photochemically formed, were typically 20–30%. Using these reaction efficiencies, we calculated the Br₂(g) release rate from aged, ambient sea-salt particles due to OH oxidation to be approximately 0.07 pptv h⁻¹ with the main contributions from nitrate photolysis and partitioning of gas-phase OH into the particle. While our solution conditions are simplified compared to ambient particles, this estimated rate of Br₂ release is high enough to suggest that OH-mediated reactions in sea-salt particles could be a significant source of reactive bromine to the marine boundary layer.     

Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm³ molecule⁻¹ s⁻¹): k₁(OH+CH₂CHC(O)OH)=(1.75±0.47)×10⁻¹¹, k₂(Cl+CH₂CHC(O)OH)=(3.99±0.84)×10⁻¹⁰, k₃(OH+CH₂CHCN)=(1.11±0.33)×10⁻¹¹ and k₄(Cl+CH₂CHCN)=(1.11±0.23)×10⁻¹⁰ with uncertainties representing ±2σ. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds.     

Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO2 aqueous solution

5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO₂ heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.     

Effects of manganese-toxicity on immune-related organs of cocks

Manganese (Mn) is a trace element known to be essential for maintaining the proper function and regulation of many biochemical and cellular reactions. However, little is known about the effect of excessive amounts of Mn in immune damage of birds. The aim of this study was to investigate the effect of dietary Mn on immune damage in birds. 50-day-old male Hy-line cocks were fed either a commercial diet or a Mn-supplemented diet containing 600, 900, and 1800 mg kg^?1 MnCl₂. After being treated with Mn for 30, 60 and 90 d, the serum and immune organs (spleen, thymus, and bursa of Fabricius (BF)) were collected respectively and examined for Mn contents, activities of superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px), malondialdehyde (MDA) contents, ability to resist OH. In addition, DNA damage and apoptosis were observed in cock immune system treated with Mn. The results showed that the contents of Mn and MDA in immune organs and serum were increased, while the activities of SOD, GSH-Px, and ability to resist OH were decreased in the Mn treatment groups. The extensive damage was observed in the immune organs. DNA single strand break and DNA–protein crosslink showed time and dosage effect in lymphocytes of immune organs. It indicated that Mn exposure resulted in oxidative damage of birds immune system by altering antioxidant defense enzyme systems, lipid peroxidation, and apoptosis.     

Laboratory studies of the impact of aerosol composition on the heterogeneous oxidation of 1-propanol

The effects of (NH₄)₂SO₄, NH₄NO₃, NaCl, NH₄Cl, and Na₂SO₄ aerosols on the kinetics of 1-propanol oxidation in the presence of the hydroxyl radical have been investigated using the relative rate technique. p-Xylene was used as a reference compound. Two different aerosol concentrations that are typical of polluted urban conditions were tested. The total surface areas of aerosols were 1400 (condition I) and 3400 μm² cm⁻³ (condition II). Results indicate that aerosols promote the oxidation of 1-propanol, and the extents of the promoting effects depend on the aerosol composition and concentration. Increases in the relative rates of the 1-propanol/OH reaction vs. the p-xylene/OH reaction were only observed for (NH₄)₂SO₄ aerosol conditions I and II, NH₄NO₃ aerosol condition II, and NH₄Cl aerosol condition II. These results indicate that NH₄⁺ is the species promoting the oxidation of 1-propanol, and suggests the possibility of a strong interaction between NH₄⁺ and 1-propanol that can change the activation energy of the initial OH attack. These results have profound implications on the use of air quality models for the assessment of air pollution control strategies.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Kinetic aspects and identification of by-products during the ozonation of bitertanol in agricultural wastewaters

The degradation of bitertanol by ozone treatment is investigated. Solutions of bitertanol (8.4 μg mL^?1) were prepared either by dissolution of the standard or by dilution of Gaucho Blé seed loading solution and then ozonated under different conditions. Evolution of the concentrations of bitertanol and its ozonation by-products in both solutions was monitored by HPLC–UV as a function of the treatment time for a concentration of 100 g m^?3 of ozone in the inlet gas. Bitertanol degradation was found to follow a pseudo-first order reaction in both cases. However, the rate of the reaction in diluted seed loading solution was much lower (0.19 vs. 0.27 min^?1 in standard solution) and was close to the reaction rate observed in the presence of a radical scavenger, tert-butanol (0.11 min^?1). Thus, it may be suggested that additives present in the seed loading solution may play the role of radical scavengers. Study of ozone concentration in the inlet gas (from 25 to 100 g m^?3) showed that ozone degradation is also a first-order reaction with respect to ozone. Four ozonation by-products were highlighted, collected and identified by HPLC coupled with an ion trap mass spectrometer using positive electrospray ionization mode. A degradation pathway of bitertanol was finally proposed.     

The sensitivity of the CHIMERE model to emissions reduction scenarios on air quality in Northern Italy

The sensitivity of the CHIMERE model to emission reduction scenarios on particulate matter PM2.5 and ozone (O₃) in Northern Italy is studied. The emissions of NO_x, PM2.5 SO₂, VOC or NH₃ were reduced by 50% for different source sectors for the Lombardy region, together with 5 additional scenarios to estimate the effect of local measures on improving the air quality for the Po valley area. Firstly, we evaluate the model performance by comparing calculated surface aerosol concentrations for the standard case (no emission reductions) with observations for January and June 2005. Calculated monthly mean PM10 concentrations are in general underestimated. For June, modelled PM10 concentrations slightly overestimate the measurements. Calculated monthly mean SO₄, NO₃^?, NH₄⁺ concentrations are in good agreement with the observations for January and June. Secondly, the model sensitivity of emission reduction scenarios on PM2.5 and O₃ calculated concentrations for the Po valley area is evaluated. The most effective scenarios to abate PM2.5 concentration are based on the SNAP2 (non-industrial combustion plants) and SNAP7 (road traffic) sectors, for which the NO_x and PM2.5 emissions are reduced by 50%. The number of days that the 2015 PM2.5 limit value of 25 μg m^?3 in Milan is exceeded by reducing primary PM2.5 and NO_x emissions for SNAP2 and 7 by 50%, does not change in January when compared to the standard case for the Milan area. It appears that 40% of the PM2.5 concentration in the greater Milan area is caused by the emissions surrounding the Lombardy region and from the model boundary conditions.This study also showed that a more effective pollutant reduction (emissions) per ton of pollutant reduced (concentrations) for the greater Milan area is obtained by reducing the primary PM2.5 emissions for SNAP7 by 50%. The most effective scenario on PM2.5 decrease for which precursor emissions are reduced is achieved by reducing SO₂ emissions by 50% for SNAP7.Our study showed that during summer time, the largest reductions in O₃ concentrations are achieved for SNAP7 emission reductions, when volatile organic compounds (VOCs) are reduced by 50%.     

Estimated photochemical ozone creation potentials (POCPs) of CF3CFCH2 (HFO-1234yf) and related hydrofluoroolefins (HFOs)

The photochemical ozone creation potentials (POCPs) for CF₃CFCH₂ and other commercially significant hydrofluoroolefins have been estimated for the first time. CF₃CFCH₂ (HFO-1234yf) has a POCP of 7.0 which is less than that for ethane (12.3) and greater than for methane (0.6). Methane and ethane have sufficiently low POCPs that they are usually considered unreactive with respect to ozone formation in urban areas and accordingly are exempt from volatile organic compound (VOC) emission regulations. Estimated POCPs for other hydrofluoroolefins are: CH₂CF₂, 18.0; CF₂CF₂, 12.5; CH₂CHCF₃, 10.7; CF₂CFCF₃, 5.4; Z-CHFCFCF₃, 5.6; E-CHFCFCF₃, 7.3; CH₂CHCF₂CF₃, 6.6; and t-CHFCHCF₃, 6.4.     

Surface ozone-temperature relationships in the eastern US: A monthly climatology for evaluating chemistry-climate models

We use long-term, coincident O₃ and temperature measurements at the regionally representative US Environmental Protection Agency Clean Air Status and Trends Network (CASTNet) over the eastern US from 1988 through 2009 to characterize the surface O₃ response to year-to-year fluctuations in weather, for the purpose of evaluating global chemistry-climate models. We first produce a monthly climatology for each site over all available years, defined as the slope of the best-fit line (m_O3-T) between monthly average values of maximum daily 8-hour average (MDA8) O₃ and monthly average values of daily maximum surface temperature (T_max). Applying two distinct statistical approaches to aggregate the site-specific measurements to the regional scale, we find that summer time m_O3-T is 3–6 ppb K^?1 (r = 0.5–0.8) over the Northeast, 3–4 ppb K^?1 (r = 0.5–0.9) over the Great Lakes, and 3–6 ppb K^?1 (r = 0.2–0.8) over the Mid-Atlantic. The Geophysical Fluid Dynamics Laboratory (GFDL) Atmospheric Model version 3 (AM3) global chemistry-climate model generally captures the seasonal variations in correlation coefficients and m_O3-T despite biases in both monthly mean summertime MDA8 O₃ (up to +10 to +30 ppb) and daily T_max (up to +5 K) over the eastern US. During summer, GFDL AM3 reproduces m_O3-T over the Northeast (m_O3-T = 2–6 ppb K^?1; r = 0.6–0.9), but underestimates m_O3-T by 4 ppb K^?1 over the Mid-Atlantic, in part due to excessively warm temperatures above which O₃ production saturates in the model. Combining T_max biases in GFDL AM3 with an observation-based m_O3-T estimate of 3 ppb K^?1implies that temperature biases could explain up to 5–15 ppb of the MDA8 O₃ bias in August and September though correcting for excessively cool temperatures would worsen the O₃ bias in June. We underscore the need for long-term, coincident measurements of air pollution and meteorological variables to develop process-level constraints for evaluating chemistry-climate models used to project air quality responses to climate change.