Atmospheric degradation of fluoroesters (FESs): Gas-phase reactivity study towards OH radicals at 298 K

Using the relative technique, rate coefficients have been measured for the gas phase reactions of hydroxyl radicals with four fluoroacetates, methyl trifluoroacetate (CF₃COOCH₃), ethyl trifluoroacetate (CF₃COOCH₂CH₃), methyl difluoroacetate (CF₂HCOOCH₃) and 2,2,2-trifluoroethyl trifluoroacetate (CF₃COOCH₂CF₃). Experiments were carried out at 296±2 K and atmospheric pressure (∼750 Torr) using nitrogen or synthetic air as bath gases. The following rate coefficients were derived for the reaction of OH radicals (in units of cm³ mol⁻¹ s⁻¹) with CF₃COOCH₃, k=(4.97±1.04)×10⁻¹⁴, CF₃COOCH₂CH₃, k=(2.64±0.59)×10⁻¹³, CF₂HCOOCH₃, k=(1.48±0.34)×10⁻¹³ and CF₃COOCH₂CF₃, (1.05±0.23)×10⁻¹³. The rate constants obtained are compared with previous literature data of other volatile organic compounds to establish reactivity trends. Atmospheric implications are discussed in terms of lifetimes and fates of the fluoroacetates in the troposphere.     

The rate and mechanism of the gas-phase oxidation of hydroxyacetone

The rate and mechanism for gas-phase destruction of hydroxyacetone, CH₃C(O)CH₂OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue-shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7±0.6) ×10^-20 cm² molecule^-1. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ>290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0±0.7)×10^-12 cm³ molecule^-1 s^-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6±0.7)×10^-11 cm³ molecule^-1 s^-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.     

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.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

Winter-grazing reduces methane uptake by soils of a typical semi-arid steppe in Inner Mongolia,China

Steppe ecosystems are regarded as an important sink of atmospheric methane (CH₄) and grazing is hypothesized to reduce CH₄ uptake. However, firm experimental evidence is required to prove this hypothesis. Using a fully automated, chamber-based measuring system, we conducted continuous high-frequency (at a 3-h interval) measurements of CH₄ uptake in a Leymus chinensis steppe, which is a typical grassland ecosystem in Inner Mongolia, China. Two management regimes were investigated: ungrazed since 1999 (UG99) and winter-grazed since 2001 (WG01). Measurements were carried out continuously during the periods of June–September 2004, May–September 2005 and March–June 2006. During all of these periods, significantly lower mean CH₄ uptake (±S.E.) at WG01 (28±0.7 μg C m⁻² h⁻¹) as compared to UG99 (56±1.0 μg C m⁻² h⁻¹) (p<0.01) was found. Total CH₄ uptake during the growing seasons (May–September) 2004 and 2005 at WG01 and UG99 was quantified as 1.15 and 2.15 kg C ha⁻¹, respectively. Annual rates of CH₄ uptake were approximately 1.91 (WG01) and 3.58 kg C ha⁻¹ (UG99), respectively. These results indicate that winter-grazing of steppe significantly reduced atmospheric CH₄ uptake by ca. 47%. The winter-grazing practice may have inhibited CH₄ uptake by (a) increasing the likelihood of physiological water stress for CH₄-consuming bacteria during dry periods, (b) decreasing gas diffusion into the soil and, (c) reducing the populations of CH₄ oxidizing bacteria. These three mechanisms could have collectively or independently facilitated the observed inhibitory effects. Our results suggest that grazing exerts a considerable negative impact on CH₄ uptake in semi-arid steppes at regional scales. Notwithstanding, further studies involving year-round, intensive measurements of CH₄ uptake are needed.     

Methane emissions from lakes and floodplains in Pantanal,Brazil

To evaluate the tropical wetlands contribution to the methane (CH₄) burden better, field campaigns were performed during 2004 and 2005 near the Miranda River, in five sites inside the Brazilian Pantanal region. The CH₄ fluxes were determined using the static chamber technique. Environmental variables that may affect CH₄ emissions, as the water depth, the water and air temperatures were also measured. The overall average of the 320 individual CH₄ flux measurements made between March/2004 and March/2005 was 142±314 mg CH₄ m⁻² d⁻¹, which is a value near the ones observed in other tropical flooded regions. About 47% of the fluxes measurements presented nonlinear increases in the chamber concentrations, which were assumed to be linked to CH₄ losses through bubbles. The bubble flux represented about 90% of the total CH₄ losses in the measurements and ranged from 1 to 2187 mg CH₄ m⁻² d⁻¹ with an average of 292±410 mg CH₄ m⁻² d⁻¹ (median: 153 mg CH₄ m⁻² d⁻¹). The diffusive flux ranged from 1 to 124 mg CH₄ m⁻² d⁻¹, with an average of 10±17 mg CH₄ m⁻² d⁻¹ (median: 5 mg CH₄ m⁻² d⁻¹). The fluxes from lakes were smaller than those observed in the floodplains, where the flooding was more dependent on the seasonal cycle. The diffusive flux showed a slight, but not statistically significant seasonal variation, following the seasonal variation of the flooding of the Pantanal region. A rough estimative of the total annual CH₄ emission shows that the contribution of the Pantanal is about 3.3 Tg CH₄ yr⁻¹, which represents about 3.3% of the total CH₄ emissions estimated to be originated in wetlands ecosystems. It may be a conservative estimate, which may present a large interannual variation, since it was obtained during one of the lowest flood of the Pantanal in recent years.     

Characterization of emissions from portable household combustion devices: particle size distributions,emission rates and factors,and potential exposures

A series of source tests were conducted to characterize emissions of particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO₂), methane (CH₄), and total hydrocarbon (THC ) from five types of portable combustion devices. Tested combustion devices included a kerosene lamp, an oil lamp, a kerosene space heater, a portable gas range, and four unscented candles. All tests were conducted either in a well-mixed chamber or a well-mixed room, which enables us to determine emission rates and emission factors using a single-compartment mass balance model. Particle mass concentrations and number concentrations were measured using a nephelometric particle monitor and an eight-channel optical particle counter, respectively. Real-time CO concentrations were measured with an electrochemical sensor CO monitor. CO₂, CH₄, and THC were measured using a GC-FID technique. The results indicate that all particles emitted during steady burning in each of the tested devices were smaller than 1.0 μm in diameter with the vast majority in the range between 0.1 and 0.3 μm. The PM mass emission rates and emission factors for the tested devices ranged from 5.6±0.1 to 142.3±40.8 mg h⁻¹ and from 0.35±0.06 to 9.04±4.0 mg g⁻¹, respectively. The CO emission rates and emission factors ranged from 4.7±3.0 to 226.7±100 mg h⁻¹ and from 0.25±0.12 to 1.56±0.7 mg g⁻¹, respectively. The CO₂ emission rates and emission factors ranged from 5500±700 to 210,000±90,000 mg h⁻¹ and from 387±45 to 1689±640 mg g⁻¹, respectively. The contributions of CH₄ and THC to emission inventories are expected to be insignificant due both to the small emission factors and to the relatively small quantity of fuel consumed by these portable devices. An exposure scenario analysis indicates that every-day use of the kerosene lamp in a village house can generate fine PM exposures easily exceeding the US promulgated NAAQS for PM_2.5.     

Air–land exchanges of CO2, CH4 and N2O measured by FTIR spectrometry and micrometeorological techniques

Micrometeorological flux-gradient and nocturnal boundary layer methods were combined with Fourier transform infrared (FTIR) spectroscopy for high-precision trace gas analysis to measure fluxes of the trace gases CO₂, CH₄ and N₂O between agricultural fields and the atmosphere. The FTIR measurements were fully automated and routinely obtained a precision of 0.1–0.2% for several weeks during a measurement campaign in October 1995. In flux-gradient measurements, vertical profiles of the trace gases were measured every 30 min from the ground to 22 m. When combined with independent micrometeorological measurements of water vapour fluxes, trace gas fluxes from the underlying surface could be determined. In the nocturnal boundary layer method the rate of change in mass storage in the 0–22 m layer was combined with fluxes measured at 22 m to estimate surface fluxes. Daytime fluxes for CO₂ were −0.78±0.40 (1σ) mg CO₂ m⁻² s⁻¹. Daytime fluxes of N₂O and CH₄ were very small and difficult to measure reliably using the flux-gradient technique, despite the high precision of the concentration measurements. Mean daytime flux for N₂O was 17±48 ng N m⁻² s⁻¹, while the corresponding flux for CH₄ was 47±410 ng CH₄ m⁻² s⁻¹. The mean nighttime flux of CO₂ estimated using the nocturnal boundary layer method was +0.15±0.05 mg CO₂ m⁻² s⁻¹, in good agreement with chamber measurements of respiration rates. Nighttime fluxes of CH₄ and N₂O from the nocturnal boundary layer method were 109±69 ng CH₄ m⁻² s⁻¹ and 2±3.2 ng N m⁻² s⁻¹, respectively, in good agreement with chamber measurements and inventory estimates based on the sheep and cattle stocking rates in the region. The suitability of FTIR-based methods for long term monitoring of spatially and temporally averaged flux measurements is discussed.     

A PLP–LIF kinetic study of the atmospheric reactivity of a series of C4–C7 saturated and unsaturated aliphatic aldehydes with OH

Absolute rate coefficients for the reaction of OH radical with a series of saturated and unsaturated aliphatic aldehydes were measured with the pulsed laser photolysis/laser-induced fluorescence technique at room temperature and as a function of total pressure (p_T=100–400 Torr). No pressure dependence of the rate coefficients was observed. The weighted average values obtained, k_OH±2σ, in units of 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, were 2.88±0.26 for n-butanal, 2.48±0.24 for n-pentanal, 2.60±0.21 for n-hexanal, 2.96±0.23 for n-heptanal, 3.51±0.71 for crotonaldehyde, 2.35±0.32 for trans-2-pentenal, 2.95±0.45 for trans-2-hexenal and 2.45±0.30 for trans-2-heptenal, respectively. The results are compared with previous data when available and with the corresponding coefficients for the reactions with NO₃ and O₃. The dominant tropospheric chemical loss process for these aliphatic aldehydes is the daytime reaction with OH, except in the case of trans-2-heptenal where the estimated lifetime for the reaction with NO₃ radical is smaller than the corresponding value for the OH reaction.     

Relative rate measurements of reactions of unsaturated alcohols with atomic chlorine as a function of temperature

The kinetics of two structurally similar unsaturated alcohols, 3-butene-2-ol and 2-methyl-3-butene-2-ol (MBO232), with Cl atoms have been investigated for the first time, as a function of temperature using a relative method. As far as we know, the present work also provides the first value for 3-buten-2-ol. The coefficient at room temperature was also obtained for 2-propene-1-ol (allyl alcohol). The reactions were investigated using a 400 L Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID) detection. The experiments were performed at atmospheric pressure and at temperatures between 256 and 298 K in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions, k_MBO232=(2.83±2.50)×10⁻¹⁴ exp (2670±249)/T, k_3-buten-2-ol=(0.65±1.60)×10⁻¹⁵ exp (3656±695)/T (in units of cm³ molecule⁻¹ s⁻¹). Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO₃ radicals.     

Atmospheric alcohols and aldehydes concentrations measured in Osaka,Japan and in Sao Paulo,Brazil

The use of alcohol fuel has received much attention since 1980s. In Brazil, ethanol-fueled vehicles have been currently used on a large scale. This paper reports the atmospheric methanol, ethanol and isopropanol concentrations which were measured from May to December 1997, in Osaka, Japan, where alcohol fuel was not used, and from 3 to 9 February 1998, in Sao Paulo, Brazil, where ethanol fuel was used. The alcohols were determined by the alkyl nitrite formation reaction using gas chromatography (GC-ECD) analysis. The concentration of atmospheric alcohols, especially ethanol, measured in Sao Paulo were significantly higher than those in Osaka. In Osaka, the average concentrations of atmospheric methanol, ethanol, and isopropanol were 5.8±3.8, 8.2±4.6, and 7.2±5.9 ppbv, respectively. The average ambient levels of methanol, ethanol, and isopropanol measured in Sao Paulo were 34.1±9.2, 176.3.±38.1, and 44.2±13.7 ppbv, respectively. The ambient levels of aldehydes, which were expected to be high due to the use of alcohol fuel, were also measured at these sampling sites. The atmospheric formaldehyde average concentration measured in Osaka was 1.9±0.9 ppbv, and the average acetaldehyde concentration was 1.5±0.8 ppbv. The atmospheric formaldehyde and acetaldehyde average concentrations measured in Sao Paulo were 5.0±2.8 and 5.4±2.8 ppbv, respectively. The C₂H₅OH/CH₃OH and CH₃CHO/HCHO were compared between the two measurement sites and elsewhere in the world, which have already been reported in the literature. Due to the use of ethanol-fueled vehicles, these ratios, especially C₂H₅OH/CH₃OH, are much higher in Brazil than these measured elsewhere in the world.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Methane emission from free-ranging sheep: a comparison of two measurement methods

Methane emissions from a flock of 14, 1-year old sheep grazing on a grass and legume pasture were measured using a micrometeorological mass-balance method and a sulphur hexaflouride (SF₆) tracer technique. The former measured the mean emission, over 45 min intervals, from all the sheep within a fenced 24 m×24 m enclosure, from the enrichment of methane (CH₄) in air as it passed over the sheep. The tracer technique measured emissions from a subset of 7 individual animals over 24 h periods from measurements of CH₄ and SF₆ concentrations in air exhaled by the sheep, and from the known rate of release of SF₆ from small permeation tubes placed in the animals’ rumens. Both methods gave highly similar results for 4 out of 5 days. When the species composition of dietary intake was steady during the last two days of measurement, the mean emission rate from the mass-balance method was 11.9±1.5 (SEM) g CH₄ sheep^-1 d^-1, while the rate from the tracer technique was 11.7±0.4 (SEM) g CH₄ sheep^-1 d^-1. These rates are for sheep with mean live mass of 27 kg, with a measured dry matter intake of 508 g sheep^-1 d^-1 and pasture dry matter digestibility of 69.5%. There was close agreement between these measurements and estimates from algorithms used to predict methane emissions from sheep for the Australian National Greenhouse Gas Inventory.     

Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China

Carbonyl compounds in urban ambient air and street canyons were measured from December 2008 to August 2009 in a mountainous city in southwest China (Guiyang). The formaldehyde yield from the photo-oxidation of isoprene emitted by vegetation was estimated to be in the range of 0.63–3.62 μg m^?3 from May to August, which accounted for 28.8–33.4% of ambient formaldehyde. Based on the calculation of photolysis rates and rates of reaction with the OH radical, it was found that photolysis was the predominant sink for formaldehyde and acetone in both summer and winter. For acetaldehyde, photo-oxidation by OH radicals and photolysis were the major sinks in summer while photo-oxidation by OH radicals was the dominant sink in winter. Wet precipitation was found to be an important removal process for the atmospheric carbonyls. In the urban ambient air, the average concentrations of formaldehyde, acetaldehyde, acetone and all carbonyls were 4.8 ± 2.1, 5.7 ± 3.3, 5.1 ± 2.5, and 25.1 ± 9.2 μg m^?3 (n = 139), respectively. The average concentrations of these species in street canyons were 18.8 ± 6.5, 9.4 ± 3.2, 10.9 ± 2.1, and 64.1 ± 16.3 μg m^?3 (n = 62), respectively. The significantly higher carbonyl levels on weekdays (compared to weekends) highlight the contribution of vehicle emissions to carbonyls in the street canyons.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Methane emissions from an anaerobic swine lagoon

Gaseous methane (CH₄) emissions from a swine waste holding lagoon were determined periodically during the year. Micrometeorological techniques were used in order that emission rates from the lagoon were measured under ambient conditions with little disturbance to the natural environment. During the cold winter measurement period, CH₄ fluxes were linearly related to lagoon water temperature below 22°C (r=0.87). During warmer measurement periods, both water and air temperatures and windspeed affected emissions rates. In general, flux rates followed a diurnal pattern with greater fluxes during the day when both temperature and windspeed were greatest. Mathematical models using air and water temperature and windspeed factors could explain 47 to 75% of the variation in fluxes. Daily emission rates ranged from 1 to 500 kg CH₄ ha⁻¹ d⁻¹. The average flux for the year was 52.3 kg CH₄ ha⁻¹ d⁻¹ which corresponded to about 5.6 kg CH₄ animal⁻¹ yr⁻¹ from the primary lagoon.     

Roadside BTEX and other gaseous air pollutants in relation to emission sources

Hourly concentrations of benzene, toluene, ethylbenzene, m,p-xylenes, and o-xylene (BTEX) plus CO, NO_x, SO₂ were monitored at roadsides simultaneously with the traffic volume during the dry season of 2004, in Hanoi, Vietnam. The selected three streets included Truong Chinh (TC) with high traffic volume, Dien Bien Phu (DBP) with low traffic volume, and Nguyen Trai (NT) with high traffic volume running through an industrial estate. BTEX were sampled by SKC charcoal tubes and analyzed by GC–FID. Geometric means of hourly benzene, toluene, ethylbenzene, m,p-xylenes and o-xylene are, respectively, 65, 62, 15, 43, and 22 μg m⁻³ in TC street; 30, 38, 9, 26, and 13 μg m⁻³ in DBP street; and 123, 87, 24, 56, and 30 μg m⁻³ in NT street. Levels of other gaseous pollutants including CO, NO_x, and SO₂, measured by automatic instruments, were low and not exceeding the Vietnam national ambient air quality standards. BTEX levels were comparatively analyzed for different downwind distances (3–50 m) from the street, between peak hours and off-peak hours, as well as between weekdays and weekend. Results of principal component analysis suggest that the gaseous pollutants are associated with different vehicle types.     

OH and HO2 measurements in a forested region of north-western Greece

Boundary layer concentrations of hydroxyl (OH) and hydroperoxyl (HO₂) radicals were measured at 1180 m elevation in a mountainous, forested region of north-western Greece during the AEROsols formation from BIogenic organic Carbon (AEROBIC) field campaign held in July–August 1997. In situ measurements of OH radicals were made by laser-induced fluorescence (LIF) at low pressure, exciting in the (0, 0) band of the A–X system at 308 nm. HO₂ radicals were monitored by chemical titration to OH upon the addition of NO, with subsequent detection by LIF. The instrument was calibrated regularly during the field campaign, and demonstrated a sensitivity towards OH and HO₂ of 5.2×10⁵ and 2.4×10⁶ molecule cm⁻³, respectively, for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Diurnal cycles of OH and HO₂ were measured on 10 days within a small clearing of a forest of Greek Fir (Abies Borisi-Regis). In total 4165 OH data points and 1501 HO₂ data points were collected at 30 s intervals. Noon-time OH and HO₂ concentrations were between 4–12×10⁶ and 0.4–9×10⁸ molecule cm⁻³, respectively. The performance of the instrument is evaluated, and the data are interpreted in terms of correlations with controlling variables. A significant correlation (r²=0.66) is observed between the OH concentration and the rate of photolysis of ozone, J(O¹D). However, OH persisted into the early evening when J(O¹D) had fallen to very low values, consistent with the modelling study presented in the following paper (Carslaw et al., 2001, OH and HO₂ radical chemistry in a forest region of north-western Greece. Atmospheric Environment 35, 4725–4737) that predicts a significant radical source from the ozonolysis of biogenic alkenes. Normalisation of the OH concentrations for variations in J(O¹D) revealed a bell-shaped dependence of OH upon NO_x (NO+NO₂), which peaked at [NO_x] ∼1.75 ppbv. The diurnal variation of HO₂ was found to be less correlated with J(O¹D) compared to OH.