Methylchloroform: Global distribution,seasonal cycles,and anthropogenic chlorine

It is evident that the global concentrations of methylchloroform (CH₃CCl₃) are increasing although at much lower rates than in the past. The ratio of concentrations in the two hemispheres has varied and is now declining, which reflects the constancy of the industrial emissions over the past 5 years. Observations show that the mid-latitude concentrations in both hemispheres are slightly lower during the summer than at other times, probably reflecting the greater removal of CH₃CCl₃ by OH radicals during summer. Calculations show that the lifetime of CH₃CCl₃ is about 6 (±1.5) years, which is considerably shorter than many previous estimates. It implies that there are probably 8 × 10⁵ molecules of OH/cm₃ of air, although this estimate may be uncertain by ±75%. The shorter lifetime is partly due to a revision of the estimated absolute concentration of CH₃CCl₃ in the atmosphere, which was found to be about 20% less than estimated previously. The relatively short lifetime suggests that in the future CH₃CCl₃ will contribute <15% of the anthropogenic chlorine in the troposphere, which is an approximate measure of its relative contribution to the depletion of the stratospheric ozone layer.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Identification and quantification of methyl halide sources in a lowland tropical rainforest

In conjunction with the OP3 campaign in Danum Valley, Malaysian Borneo, flux measurements of methyl chloride (CH₃Cl) and methyl bromide (CH₃Br) were performed from both tropical plant branches and leaf litter in June and July 2008. Live plants were mainly from the Dipterocarpaceae family whilst leaf litter samples were representative mixtures of different plant species. Environmental parameters, including photosynthetically-active radiation, total solar radiation and air temperature, were also recorded. The dominant factor determining magnitude of methyl halide fluxes from living plants was plant species, with specimens of the genus Shorea showing persistent high emissions of both gases, e.g. Shorea pilosa: 65 ± 17 ng CH₃Cl h^?1 g^?1 (dry weight foliage) and 2.7 ± 0.6 ng CH₃Br h^?1 g^?1 (dry weight foliage). Mean CH₃Cl and CH₃Br emissions across 18 species of plant were 19 (range, <LOD ?76) and 0.4 (<LOD ?2.9) ng h^?1 g^?1 respectively; fluxes from leaf litter were 1–2 orders of magnitude smaller per dry mass. CH₃Cl and CH₃Br fluxes were weakly correlated. Overall, the findings suggest that tropical rainforests make an important contribution to global terrestrial emissions of CH₃Cl, but less so for CH₃Br.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Measurement of methyl halides in the marine atmosphere

An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH₃Cl, CH₃Br, and CH₃I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH₃Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH₃Cl concentration amounted to as high as 1400 pptv and indicated that CH₃Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH₃Br and CH₃I, suggesting a common source in the area.     

Latitudinal distributions of trace gases in and above the boundary layer

Statistical analyses of global atmospheric concentrations provide evidence that C₂Cl₄, CHCl₃ and CH₃CCl₃ (methylchloroform) are more abundant in the tropical boundary layer than above it (α ? 0.09) by 27% (±27%), 21% (?21%, +12%) and 6.4% (±6%) respectively. The air samples on which these results are based were collected by cryogenic techniques during the June 1978 project GAMETAG flights and analyzed soon afterwards by gas chromatography (EC/GC and GC/FID), thus providing latitudinal concentrations of CO, CH₄, CCl₃F, CCl₂F₂, CH₃CCl₃ and light C₂-hydrocarbons, both in and above the boundary layer. In August 1980, after further development of analytical techniques, the stored air samples were re-analyzed to establish the latitudinal distributions of CH₃I, CHCl₃, C₂Cl₄, C₂F₃Cl₃ (F-113) and CHClF₂ (F-22) in and above the boundary layer. Stability studies, spanning a year, show that the concentrations of these gases do not change in the flasks.     

Rate Constants for the Reaction of OH with Halocarbons in the Presence of O2 + N2

Rates of CO₂ production in the reaction CO + OH and CO + OH + halocarbon have been used to determine rate constants for some OH + halocarbon reactions at 29.5°C relative to that of k(CO + OH) = 2.69 × 10^?13 cm³ molecule^?1 sec^?1. The following rate constants were obtained: k(OH + CH₃Cl) = 3.1 ± 0.8, k(OH + CH₂Cl₂) = 2.7 ± 1.0, k(OH + C₂H₅Cl) = 44.0 ± 25, k(OH + CICH₂CH₂CI) = 6.5, (<29) and k(OH + CH₃CCl₃) = 2.1 (<5.7) cm³ molecule^?1 sec^?1 × 10^?14. The k values, CH₂Cl₂ excepted, are in substantial agreement with determinations made in nonoxygen environments. The present results for CH₂Cl₂ are almost certainly in error due to difficulties with the competitive approach used.     

Effects of ammonia on methane oxidation in landfill cover materials

The effects of ammonia (NH₃) on CH₄ attenuation in landfill cover materials consisting of landfill cover soil (LCS) and aged municipal solid waste (AMSW), at different CH₄ concentrations, were investigated. The CH₄ oxidation capacities of LCS and AMSW were found to be significantly affected by the CH₄ concentration. The maximum oxidation rates for LCS and AMSW were obtained at CH₄ concentrations of 5 % and 20 %(v/v), respectively, within 20 days. CH₄ biological oxidation in AMSW was significantly inhibited by NH₃ at low CH₄ concentrations (5 %, v/v) but highly stimulated at high levels (20 % and 50 %, v/v). Oxidation in LCS was stimulated by NH₃ at all CH₄ concentrations due to the higher conversion of the nitrogen in NH₃ in AMSW than in LCS. NH₃ increases CH₄ oxidation in landfill cover materials.     

Snowpack processing of acetaldehyde and acetone in the Arctic atmospheric boundary layer

Acetaldehyde (CH₃CHO) and acetone (CH₃C(O)CH₃) concentrations in ambient air, in snowpack air, and bulk snow were determined at Alert, Nunavut, Canada, as a part of the Polar Sunrise Experiment (PSE): ALERT 2000. During the period of continuous sunlight, vertical profiles of ambient and snowpack air exhibited large concentration gradients through the top ∼10 cm of the snowpack, implying a flux of carbonyl compounds from the surface to the atmosphere. From vertical profile and eddy diffusivity measurements made simultaneously on 22 April, acetaldehyde and acetone fluxes of 4.2(±2.1)×10⁸ and 6.2(±4.2)×10⁸ molecules cm⁻² s⁻¹ were derived, respectively. For this day, the sources and sinks of CH₃CHO from gas phase chemistry were estimated. The result showed that the snowpack flux of CH₃CHO to the atmosphere was as large as the calculated CH₃CHO loss rate from known atmospheric gas phase reactions, and at least 40 times larger (in the surface layer) than the volumetric rate of acetaldehyde produced from the assumed main atmospheric gas phase reaction, i.e. reaction of ethane with hydroxyl radicals. In addition, acetaldehyde bulk snow phase measurements showed that acetaldehyde was produced in or on the snow phase, likely from a photochemical origin. The time series for the observed CH₃C(O)CH₃, ozone (O₃), and propane during PSE 1995, PSE 1998, and ALERT 2000 showed a consistent anti-correlation between acetone and O₃ and between acetone and propane. However, our data and model simulations showed that the acetone increase during ozone depletion events cannot be explained by gas phase chemistry involving propane oxidation. These results suggest that the snowpack is a significant source of acetaldehyde and acetone to the Arctic boundary layer.     

Meridional and vertical CO and CH4 distributions in the background troposphere (70°N-60°S; 0–12 km altitude) from scientific aircraft measurements during the stratoz III experiment (June 1984)

During the STRATOZ III experiment (June 1984) designed for a study of trace gases in the atmosphere, more than 2000 concurrent measurements of CO and CH₄ by gas chromatography were obtained from a series of flights aboard a scientific aircraft “Caravelle 116” between 70°N and 60°S, and up to a cruising altitude of 12 km, over the Atlantic Ocean and along the American, African and European continents.While a global interpretation of the data must await the examination of the whole series of compounds measured, a preliminary analysis of the results obtained for CO and CH₄ is reported here.The CO and CH₄ mixing ratios are found to be higher in the Northern Hemisphere than in the Southern, which reflects the meridional distribution of their sources and the influence of tropospheric photochemistry. A prominent CO difference between the two hemispheres is observed in the continental air (NH: 100–200 ppb; SH: 80–90 ppb) while the oceanic air is much more homogeneous (NH: 80–90 ppb; SH: 60–70 ppb). In the case of CH₄, a regular decrease is observed between the high latitudes of the Northern Hemisphere and those of the Southern.For the Southern Hemisphere, the CO values are in agreement with literature data, but for the Northern they are lower than previously reported. The CH₄ results suggest the possible existence of natural sources in the Southern Hemisphere (Amazonia; South Pacific).A comparison of the measurements made in the Southern Hemisphere with reliable data sets previously reported in the literature confirms an increase rate of 1.2 ± 0.3 % per year for CH₄, but does not provide any evidence for a long term variation of the CO content.The comprehensive data reported here will be of valuable interest to improve the understanding of the physico-chemistry of the troposphere and its evolution.     

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.     

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.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Note on In-Traffic Measurement of Airborne Tire-Wear Participate Debris

Measuring greenhouse gas (GHG) source emissions provides data for validation of GHG inventories, which provide the foundation for climate change mitigation. Two Toyota RAV4 electric vehicles were outfitted with high-precision instrumentation to determine spatial and temporal resolution of GHGs (e.g., nitrous oxide, methane [CH₄], and carbon dioxide [CO₂]), and other gaseous species and particulate metrics found near emission sources. Mobile measurement platform (MMP) analytical performance was determined over relevant measurement time scales. Pollutant residence times through the sampling configuration were measured, ranging from 3 to 11 sec, enabling proper time alignment for spatial measurement of each respective analyte. Linear response range for GHG analytes was assessed across expected mixing ratio ranges, showing minimal regression and standard error differences between 5, 10, 30, and 60 sec sampling intervals and negligible differences between the two MMPs. GHG instrument drift shows deviation of less than 0.8% over a 24-hr measurement period. These MMPs were utilized in tracer-dilution experiments at a California landfill and natural gas compressor station (NGCS) to quantify CH₄ emissions. Replicate landfill measurements during October 2009 yielded annual CH₄ emissions estimates of 0.10 ± 0.01, 0.11 ± 0.01, and 0.12 ± 0.02 million tonnes of CO₂ equivalent (MTCO₂E). These values compare favorably to California GHG Emissions Inventory figures for 2007, 2008, and 2009 of 0.123, 0.125, and 0.126 MTCO₂E/yr, respectively, for this facility. Measurements to quantify NGCS boosting facility-wide emissions, during June 2010 yielded an equivalent of 5400 ± 100 TCO₂E/yr under steady-state operation. However, measurements during condensate transfer without operational vapor recovery yield an instantaneous emission rate of 2–4 times greater, but was estimated to only add 12 TCO₂E/yr overall. This work displays the utility for mobile GHG measurements to validate existing measurement and modeling approaches, so emission inventory values can be confirmed and associated uncertainties reduced.

Implications:?Measuring greenhouse gas (GHG) source emissions provides data and validation for GHG inventories, the foundation for climate change mitigation. Mobile measurement platforms with robust analytical instrumentation completed tracer-dilution experiments in California at a landfill and natural gas compressor station (NGCS) to quantify CH₄ emissions. Data collected for landfill CH₄ agree with the current California emissions inventory, while NGCS data show the possible variability from this type of facility. This work displays the utility of mobile GHG measurements to validate existing measurement and modeling approaches, such that emission inventory values can be confirmed, associated uncertainties reduced, and mitigation efforts quantified.     

Characteristics of gaseous pollutants from biofuel-stoves in rural China

The research team analyzed the emission characteristics of gaseous pollutants, including volatile organic compounds (VOCs), from biomass combustion in improved stoves in rural China. The research included measurements from five biofuels and two stove types in the months of January, April, and September. The measurements were conducted according to U.S. EPA Method 25 using a collection system with a cooling device and two-level filters. CO, CO₂, NO_x, CH₄ and THC analyzers were used for in-field, real-time emission measurements. The emission data indicate that gaseous pollutants were emitted at higher concentrations in the early combustion stage and lower concentrations in the later stage. CH₄ and THC, as well as CO and CO₂, presented positive relationships during the whole entire combustion process for all tests. The chemical profiles of flue gas samples were analyzed by GC/MS and GC/FID/ECD. Aromatics, carbonyls, and alkenes & alkynes dominated the VOC emissions, respectively accounting for 37%, 33%, and 23% of total VOC emissions by volume. Benzene was the most abundant VOC species, consisting of 17.3 ± 8.1% of VOCs, followed by propylene (11.3 ± 3.5%), acetone (10.8 ± 8.2%), toluene (7.3 ± 5.7%) and acetaldehyde (6.5 ± 7.3%). Carbon mass balance approach was applied to calculate CO, CO₂, CH₄, NO_x, and VOC species emission factors. This analysis includes a discussion of the differences among VOC emission factors of different biofuel-stove combinations.     

Sources and characteristics of carbonaceous aerosols at Agra “World heritage site” and Delhi “capital city of India”

Agra, one of the oldest cities “World Heritage site”, and Delhi, the capital city of India are both located in the border of Indo-Gangetic Plains (IGP) and heavily loaded with atmospheric aerosols due to tourist place, anthropogenic activities, and its topography, respectively. Therefore, there is need for monitoring of atmospheric aerosols to perceive the scenario and effects of particles over northern part of India. The present study was carried out at Agra (AGR) as well as Delhi (DEL) during winter period from November 2011 to February 2012 of fine particulate (PM_2.5: d?<?2.5 μm) as well as associated carbonaceous aerosols. PM_2.5 was collected at both places using medium volume air sampler (offline measurement) and analyzed for organic carbon (OC) and elemental carbon (EC). Also, simultaneously, black carbon (BC) was measured (online) at DEL. The average mass concentration of PM_2.5 was 165.42?±?119.46 μg m^?3 at AGR while at DEL it was 211.67?±?41.94 μg m^?3 which is ~27 % higher at DEL than AGR whereas the BC mass concentration was 10.60 μg m^?3. The PM_2.5 was substantially higher than the annual standard stipulated by central pollution control board and United States Environmental Protection Agency standards. The average concentrations of OC and EC were 69.96?±?34.42 and 9.53?±?7.27 μm m^?3, respectively. Total carbon (TC) was 79.01?±?38.98 μg m^?3 at AGR, while it was 50.11?±?11.93 (OC), 10.67?±?3.56 μg m^?3 (EC), and 60.78?±?14.56 μg m^?3 (TC) at DEL. The OC/EC ratio was 13.75 at (AGR) and 5.45 at (DEL). The higher OC/EC ratio at Agra indicates that the formation of secondary organic aerosol which emitted from variable primary sources. Significant correlation between PM_2.5 and its carbonaceous species were observed indicating similarity in sources at both sites. The average concentrations of secondary organic carbon (SOC) and primary organic carbon (POC) at AGR were 48.16 and 26.52 μg m^?3 while at DEL it was 38.78 and 27.55 μg m^?3, respectively. In the case of POC, similar concentrations were observed at both places but in the case of SOC higher over AGR by 24 in comparison to DEL, it is due to the high concentration of OC over AGR. Secondary organic aerosol (SOA) was 42 % higher at AGR than DEL which confirms the formation of secondary aerosol at AGR due to rural environment with higher concentrations of coarse mode particles. The SOA contribution in PM_2.5 was also estimated and was ~32 and 12 % at AGR and DEL respectively. Being high loading of fine particles along with carbonaceous aerosol, it is suggested to take necessary and immediate action in mitigation of the emission of carbonaceous aerosol in the northern part of India.     

Comparisons of ambient air particulates concentrations (TSP,PM2.5) and dry depositions during smog and non-smog periods at Luliao,Shalu District sampling site

The concentrations of ambient total suspended particulates (TSP) and PM_2.5, and the dry depositions at a sample site at Luliao Junior High School (Luliao) in central Taiwan were measured during smog and non-smog days between December 2017 and July 2018. The results are compared to those obtained during non-smog periods in the years 2015–2017. The mean TSP and PM_2.5 concentrations and dry deposition flux were 72.41?±?26.40, 41.88?±?23.51?μg/m³, and 797.57?±?731.46?μg/m² min, respectively, on the smog days. The mean TSP and PM_2.5 concentrations and dry deposition flux on the non-smog days were 56.39?±?18.08, 34.81?±?12.59?μg/m³ and 468.93?±?600.57?μg/m² min, respectively. The mean TSP concentration in the smog period was 28% greater than that in the non-smog period, and the mean PM_2.5 concentration was 20% higher. The mean dry deposition flux in the smog period was 70% higher than that in the non-smog period at Luliao. The PM_2.5 concentrations exceeded the standards set by the Taiwan EPA (35?μg/m³ daily, and 15?μg/m³ annually). Therefore, the TSP and PM_2.5 concentrations and dry deposition must be reduced in central Taiwan on smog days. In addition, atmospheric TSP and PM_2.5 concentrations at various sampling sites were compared, and those herein were not higher than those measured in other countries. Finally, apart from the local traffic emissions, during smog periods, the other pollution source originated from the transportation process of traffic pollutants emitted in the northwest side of Taiwan.     

Effect of land-use change on CH4 and N2O emissions from freshwater marsh in Northeast China

The wetlands play an important role in global carbon and nitrogen storage, and they are also natural sources of greenhouse gases such as methane (CH₄) and nitrous oxide (N₂O). Land-use change is an important factor affecting the exchange of greenhouse gases between wetlands and the atmosphere. However, few studies have investigated the effect of land-use change on CH₄ and N₂O emissions from freshwater marsh in China. Therefore, a field study was carried out over a year to investigate the seasonal changes of the emissions of CH₄ and N₂O at three sites (Deyeuxia angustifolia marsh, dryland and rice field) in the Sanjiang Plain of Northeast China. Marsh was the source of CH₄ showing a distinct temporal variation. Maximum fluxes occurred in June and the highest value was 20.69 ± 2.57 mg CH₄ m^?2 h^?1. The seasonal change of N₂O fluxes from marsh was not obvious, consisted of a series of emission pulses. The marsh acted as a N₂O sink during winter, while became a N₂O source in the growing season. The results showed that gas exchange between soil/snow and the atmosphere in the winter season contributed greatly to the annual budgets. The winter season CH₄ flux was about 3.24% of the annual flux and the winter uptake of N₂O accounted for 13.70% of the growing-season emission. Conversion marsh to dryland resulted in a shift from a strong CH₄ source to a weak sink (from 199.12 ± 39.04 to ?1.37 ± 0.68 kg CH₄ ha^?1 yr^?1), while increased N₂O emissions somewhat (from 4.07 ± 1.72 to 4.90 ± 1.52 kg N₂O ha^?1 yr^?1). Conversion marsh to rice field significantly decreased CH₄ emission from 199.12 ± 39.04 to 94.82 ± 9.86 kg CH₄ ha^?1 yr^?1 and N₂O emission from 4.07 ± 1.72 to 2.09 ± 0.79 kg N₂O ha^?1 yr^?1.     

Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

The Fate and Behavior of Mercury in Coal-Fired Power Plants

Abstract

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 ± 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 ± 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%.

On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only ~3 μg/m_STP ³ at 6% O₂. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing.

Speciation of Hg is a very important factor. An oxidized form (HgCl₂) favors a high degree of removal. The conversion from Hg⁰ to HgCl₂ is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.