Modelling the multiphase near-surface chemistry related to ozone depletions in polar spring

Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br₂, BrCl, or Cl₂ to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H₂O₂, DMS, Cl₂, C₂H₆, HONO, NO₂, and RONO₂ was investigated. Cases with elevated mixing ratios of HCHO, H₂O₂, DMS, Cl₂, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C₂H₆ induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NO_y species studied (HONO, NO₂, RONO₂) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NO_x. The production of HNO₃ led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl₂ or BrCl) increased.     

Relations between Light Hydrocarbon, Carbon Monoxide, and Carbon Dioxide Concentrations in the Plume from the Combustion of Plant Material in a Furnace

To systematically explain relations between light hydrocarbons, CO, and CO₂ concentrations/emissions of biomassburning, we measured concentrations/emissions of carbon gases – CO,CO₂, light hydrocarbons (CH₄, C₂H₆,C₂H₄, C₂H₂, C₃H₈, C₃H₆,n-C₄H₁₀, i-C₄H₁₀, n-C₅H₁₂,i-C₅H₁₂), and THC (total hydrocarbon) – in the burning of dead plant material, mainly Imperata grass, byclosed-chamber experiments and by time-series analyses of gas concentrations in combustion plumes in relatively efficient and inefficient combustion situations. Concentrations of hydrocarbons measured were well correlated to [CO] although [C₂H₂] was exceptionally well correlated to[CO₂]. The phase diagrams (relation between [CO]/ [CO₂] and [hydrocarbon]/ [CO₂]) obtained by the time-seriesexperiments well illustrated the variation in the overall emission rates of the closed-chamber experiments. The higher rates of decrease in hydrocarbon concentration with increasing carbon number in the efficient case compared with the inefficient case probably reflected the rate of oxidation and the amount of radicals. The overall concentrations (or emissions) of C₂H₄ and C₃H₆ were higher thanthose of C₂H₆ and C₃H₈, suggesting a linkage to mechanisms in whichthe predominant path of hydrocarbon oxidation is through the degradation of alkyl radicals, which can be immediately converted into or formed from alkenes. For C₃ and C₄ species, normal-chain species hadhigher emissions than iso-chain species under lower combustion efficiency. This may be attributable to the presence of tertiary C–H bonds in iso-species,which show more reactivity in the abstraction of H than secondary C–H bonds unless the carbon number is large.     

Regional Sources of Methyl Chloride, Chloroform and Dichloromethane Identified from AGAGE Observations at Cape Grim, Tasmania, 1998–2000

There are large uncertainties in identifying and quantifying the natural and anthropogenic sources of chloromethanes – methyl chloride (CH₃Cl), chloroform (CHCl₃) and dichloromethane (CH₂Cl₂), which are responsible for about 15% of the total chlorine in the stratosphere. We report two years of in situ observations of these species from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41° S, 145° E). The average background levels of CH₃Cl, CHCl₃ and CH₂Cl₂ during 1998–2000 were 551± 8, 6.3± 0.2 and 8.9± 0.2 ppt (dry air mole fractions expressed in parts per 10¹²) respectively, with a two-year average amplitude of the seasonal cycles in background air of 25, 1.1 and 1.5 ppt respectively. The CH₃Cl and CHCl₃ records at Cape Grim show clear episodes of elevated mixing ratios up to 1300 ppt and 55 ppt respectively, which are highly correlated, suggesting common source(s). Trajectory analyses show that the sources of CH₃Cl and CHCl₃ that are responsible for these elevated observations are located in coastal-terrestrial and/or coastal-seawater regions in Tasmania and the south-eastern Australian mainland. Elevated levels of CH₂Cl₂ (up to 70 ppt above background) are associated mainly with emissions from the Melbourne/Port Phillip region, a large urban/industrial complex (population 3.5 million) 300 km north of Cape Grim.Now at the Centre for Atmospheric ChemistryNow at School of Environmental Sciences     

On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient

The exchange of NO₃ radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO₃ was determined on 0.1 M NaCl solutions and was found to be (NO₃) 2 × 10^-3 in good agreement with recent studies. The Henry coefficient of NO₃ was estimated to be K_H(NO₃) = 1.8 M · atm^-1, with a (2) uncertainty of ±3 M · atm^-1. From the upper limit for the Henry coefficient (K_H = 5 M · atm^-1) and available thermodynamic data, the redox potential of dissolved NO₃/NO ₃ ^– is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient K_H and the rate coefficient k ₁₀ of the potential reaction NO₃ + H₂O HNO₃ + OH. For K_H = 0.6 M · atm^-1, we find k ₁₀ < 0.05 s^-1 · atm^-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO₃ is only important under conditions where the dissolved NO₃ is removed quickly from equilibrium, for example by reactions with Cl^– or HSO ₃ ^– ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N₂O₅.     

Scenarios of possible changes in atmospheric temperatures and ozone concentrations due to man's activities,estimated with a one-dimensional coupled photochemical climate model

A one-dimensional coupled climate and chemistry model has been developed to estimate past and possible future changes in atmospheric temperatures and chemical composition due to human activities. The model takes into account heat flux into the oceans and uses a new tropospheric temperature lapse rate formulation. As found in other studies, we estimate that the combined greenhouse effect of CH₄, O₃, CF₂Cl₂, CFCl₃ and N₂O in the future will be about as large as that of CO₂. Our model calculates an increase in average global surface temperatures by about 0.6°C since the start of the industrial era and predicts for A.D. 2050 a twice as large additional rise. Substantial depletions of ozone in the upper stratosphere by between 25% and 55% are calculated, depending on scenario. Accompanying temperature changes are between 15°C and 25°C. Bromine compounds are found to be important, if no rigid international regulations on CFC emissions are effective. Our model may, however, concivably underestimate possible effects of CFCl₃, CF₂Cl₂, C₂F₃Cl₃ and other CFC and organic bromine emissions on lower stratospheric ozone, because it can not simulate the rapid breakdown of ozone which is now being observed worldwide. An uncertainty study regarding the photochemistry of stratospheric ozone, especially in the region below about 25 km, is included. We propose a reaction, involving excited molecular oxygen formation from ozone photolysis, as a possible solution to the problem of ozone concentrations calculated to be too low above 45 km. We also estimate that tropospheric ozone concentrations have grown strongly in the northern hemisphere since pre-industrial times and that further large increases may take place, especially if global emissions of NO_x from fossil fuel and biomass burning were to continue to increase. Growing NO_x emissions from aircraft may play an important role in ozone concentrations in the upper troposphere and low stratosphere.     

Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

Atmospheric ionic species in PM2.5 and PM1 aerosols in the ambient air of eastern central India

This study elucidates the characteristics of ambient PM_2.5 (fine) and PM₁ (submicron) samples collected between July 2009 and June 2010 in Raipur, India, in terms of water soluble ions, i.e. Na⁺, NH ₄ ⁺ , K⁺, Mg²⁺, Ca²⁺, Cl^?, NO ₃ ^? and SO ₄ ^2? . The total number of PM_2.5 and PM₁ samples collected with eight stage cascade impactor was 120. Annual mean concentrations of PM_2.5 and PM₁ were 150.9?±?78.6 μg/m³ and 72.5?±?39.0 μg/m³, respectively. The higher particulate matter (PM) mass concentrations during the winter season are essentially due to the increase of biomass burning and temperature inversion. Out of above 8 ions, the most abundant ions were SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ for both PM_2.5 and PM₁ aerosols; their average concentrations were 7.86?±?5.86 μg/m³, 3.12?±?2.63 μg/m³ and 1.94?±?1.28 μg/m³ for PM_2.5, and 5.61?±?3.79 μg/m³, 1.81?±?1.21 μg/m³ and 1.26?±?0.88 μg/m³ for PM₁, respectively. The major secondary species SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ accounted for 5.81%, 1.88% and 1.40% of the total mass of PM_2.5 and 11.10%, 2.68%, and 2.48% of the total mass of PM₁, respectively. The source identification was conducted for the ionic species in PM_2.5 and PM₁ aerosols. The results are discussed by the way of correlations and principal component analysis. Spearman correlation indicated that Cl^? and K⁺ in PM_2.5 and PM₁ can be originated from similar type of sources. Principal component analysis reveals that there are two major sources (anthropogenic and natural such as soil derived particles) for PM_2.5 and PM₁ fractions.     

Increases of wet deposition at remote sites in Japan from 1991 to 2009

Temporal trends in wet deposition of major ions were explored at nationwide remote sites in Japan from April 1991 to March 2009 by using the seasonal Kendall slope estimator and the nonparametric seasonal Kendall test. For the trend analysis, datasets from eight remote sites (Rishiri, Echizenmisaki, Oki, Ogasawara, Shionomisaki, Goto, Yakushima, and Amami) were selected from the Japanese Acid Deposition Survey (JADS) conducted by the Ministry of the Environment. Deposition of H⁺ has been increasing at remote sites in Japan on a national scale. Significant (p????0.05) increases in H⁺ deposition were detected with changes of +3?C+9?%?year^?1 at seven sites, while insignificant increases were observed at one site. Depositions of non-sea salt (nss)-SO ₄ ^2? and NO ₃ ^? significantly increased at four and six sites, respectively, with changes of +1?C+3?%?year^?1. Significant increases in precipitation at four sites would have contributed to the increase in depositions of H⁺, nss-SO ₄ ^2? , and NO ₃ ^? . The emission trends of SO₂ and NO_x did not corresponded to the deposition trends of nss-SO ₄ ^2? and NO ₃ ^? . The different trends indicated that temporal variation of precipitation amount trend dominated the deposition trends.     

Laboratory spectroscopic studies of atmospherically important radicals using fourier transform spectroscopy

This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm^-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the ₃ band of NO₃, at ca. 1500 cm^-1, were obtained with up to 0.005 cm^-1 resolution using the reaction between NO₂ and O₃ to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O₃, and the (1-0) vibration-rotation band in the region 829–880 cm^-1 was recorded at a resolution of 0.02 cm^-1. We were unable to observe infrared absorption of HO₂ with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N₂O₅, HNO₃, ClONO₂, FNO₂, Cl₂O, HO₂NO₂, and probably FO₂.The ability to monitor concentrations of the NO₃ radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO₂ reacts with O₃. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO₃–N₂O₅–H₂O system might be a viable source of HNO₃ in the atmosphere.     

Total column densities of tropospheric and stratospheric trace gases in the undisturbed Arctic summer atmosphere

Ground-based FTIR measurements have been performed in the Arctic summer in July 1993 and June 1994 at 79° N to study the zenith column densities of several trace gases in the undisturbed Arctic summer atmosphere. Zenith column densities of H₂O, N₂O, HNO₃, NO₂, NO, ClONO₂, ClO, HCl, HF, COF₂, OCS, SF₆, HCN, CH₄, C₂H₆, C₂H₂, CO, O₃, CFC-12, CFC-22, and CO₂ were retrieved by line-by-line calculations. The results are compared with winter and springtime observations measured at the same site, with column densities obtained in the Antarctic summer atmosphere, and with measurements at midlatitudes. For HCl the spectra give lower total zenith columns than expected, but the ratio HF/HCl agrees well with midlatitude literature data. Measurements of ClONO₂ give low total columns in agreement with observations at midlatitudes. In the undisturbed atmosphere HCl was found to be in excess of ClONO₂. The total columns of HNO₃, N₂O and the sum of NO and NO₂ agree with summer observations in Antarctica. Results for the tropospheric trace gas C₂H₆ are higher by 250% when compared with Antarctic observations. Contrary to N₂O and CH₄ the seasonal cycle of C₂H₆ and C₂H₂ give much higher total columns in winter/spring compared to the summer observations. This is assigned to transport of polluted airmasses from mid-latitudes into the Arctic.     

A three-dimensional model of the global ammonia cycle

Using a three-dimensional (3-D) transport model of the troposphere, we calculated the global distributions of ammonia (NH₃) and ammonium (NH ₄ ⁺ ), taking into account removal of NH₃ on acidic aerosols, in liquid water clouds and by reaction with OH. Our estimated global 10°×10° NH₃ emission inventory of 45 Tg N-NH₃ yr^– provides a reasonable agreement between calculated wet NH ₄ ⁺ deposition and measurements and of measured and modeled NH ₄ ⁺ in aerosols, although in Africa and Asia especially discrepancies exist.NH₃ emissions from natural continental ecosystems were calculated applying a canopy compensation point and oceanic NH₃ emissions were related to those of DMS (dimethylsulfide). In many regions of the earth, the pH found in rain and cloud water can be attributed to acidity derived from NO, SO₂ and DMS emissions and alkalinity from NH₃. In the remote lower troposphere, sulfate aerosols are calculated to be almost neutralized to ammonium sulfate (NH₄)₂SO₄, whereas in the middle and upper troposphere, according to our calculations, the aerosol should be more acidic, as a result of the oxidation of DMS and SO₂ throughout the troposphere and removal of NH₃ on acidic aerosols at lower heights. Although the removal of NH₃ by reaction with the OH radical is relatively slow, the intermediate NH₂ radical can provide a substantial annual N₂O source of 0.9 _–0.4 ^+0.9 Tg, thus contributing byca. 5% to estimated global N₂O production. The oxidation by OH of NH₃ from anthropogenic sources accounts for 10% of the estimated total anthropogenic sources of N₂O. This source was not accounted for in previous studies, and is mainly located in the tropics, which have high NH₃ and OH concentrations. Biomass burning plumes, containing high NO _x and NH₃ concentrations provide favourable conditions for gas phase N₂O production. This source is probably underestimated in this model study, due to the coarse resolution of the 3-D model, and the rather low biomass burning NH₃ and NO _x emissions adopted. The estimate depends heavily on poorly known concentrations of NH₃ (and NO _x ) in the tropics, and uncertainties in the rate constants of the reactions NH₂ + NO₂ N₂O + H₂O (R4), and NH₂ + O₃ NH₂O + O₂ (R7).     

Rainwater chemistry and bulk atmospheric deposition in a tropical semiarid ecosystem: the Brazilian Caatinga

We assessed the rainwater chemistry, the potential sources of its main inorganic components and bulk atmospheric deposition in a rural tropical semiarid region in the Brazilian Caatinga. Rainfall samples were collected during two wet seasons, one during an extremely dry year (2012) and one during a year with normal rainfall (2013). According to measurements of the main inorganic ions in the rainwater (H⁺, Na⁺, NH₄ ⁺, K⁺, Ca²⁺, Mg²⁺, Cl^?, NO₃ ^?, and SO₄ ^2?), no differences were observed in the total ionic charge between the two investigated wet seasons. However, Ca²⁺, K⁺, NH₄ ⁺ and NO₃ ^? were significant higher in the wetter year (p < 0.05) which was attributed to anthropogenic activities, such as organic fertilizer applications. The total ionic contents of the rainwater suggested a dominant marine contribution, accounting for 76 % and 58 % of the rainwater in 2012 and 2013, respectively. The sum of the non-sea-salt fractions of Cl^?, SO₄ ^2?, Mg²⁺, Ca²⁺ and K⁺ were 19 % and 33 % in 2012 and 2013, and the nitrogenous compounds accounted for 2.8 % and 6.0 % of the total ionic contents in 2012 and 2013, respectively. The ionic ratios suggested that Mg²⁺ was probably the main neutralizing constituent of rainwater acidity, followed by Ca²⁺. We observed a low bulk atmospheric deposition of all major rainwater ions during both wet seasons. Regarding nitrogen deposition, we estimated slightly lower annual inputs than previous global estimates. Our findings contribute to the understanding of rainfall chemistry in northeastern Brazil by providing baseline information for a previously unstudied tropical semiarid ecosystem.     

Estimating product yields of carbon-containing products from the atmospheric photooxidation of ambient air alkenes

The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O₃ concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO₃ radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO _x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO₃ radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO₃ radicals.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

Chemical compositions of wet precipitation and anthropogenic influences at a developing urban site in southeastern China

A comprehensive study on the chemical compositions of wet precipitation was carried out from January 2004 to December 2004 in Jinhua, southeastern China's Zhejiang Province. All samples were analyzed for pH, electrical conductivity and major ions (F⁻, Cl⁻, NO₃⁻, SO₄²⁻, K⁺, Na⁺, Ca²⁺, Mg²⁺ and NH₄⁺). The rainwater was typically acidic with a volume-weighted mean pH of 4.54, which ranged from 3.64 to 6.76. SO₄²⁻ and NO₃⁻ were the main anions, while NH₄⁺ and Ca²⁺ were the main cations. The concentrations of these major ions were generally higher compared to those reported in other parts of the world, but much lower than those in northern China.Wet deposition fluxes of major ions showed pronounced seasonal variations with maximum in spring and minimum in autumn. Significant correlations were found in soil-derived species among Ca²⁺, Mg²⁺ and K⁺ and sea-salt species between Na⁺ and Cl⁻. Other relatively good correlations were also observed between Ca²⁺ and SO₄^2-, Mg²⁺ and SO₄^2-, Mg²⁺ and NO₃⁻, Mg²⁺ and Cl⁻. Principal component analysis was also performed on individual precipitation to find possible sources of the major ionic species. Varimax rotated four components accounting for 85.9% of the total variance, and were interpreted as acid and alkaline pollutants, sea spray and mixed source, soil and acid/neutralization. Calculation of enrichment factors for rainwater components relative to soil and seawater indicated that Ca²⁺ and K⁺ mainly originated from the terrestrial source, and SO₄^2- and NO₃⁻ were mostly attributed for the anthropogenic activities in the study area. In general, the results suggested that precipitation chemistry is strongly influenced by anthropogenic sources rather than natural and marine sources. The pollutants in rainwater were mainly derived from long distance transport, local industry and traffic sources.     

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO₄ ^2–,Cl^–, F^–, NO₃ ^–, K⁺, Na⁺,NH₄ ⁺, Ca²⁺ and Mg²⁺ were determined in 11 size bins from 0.07 m to >25.5 m. The near-source size distributions showed major modes at 0.5m (SO₄ ^2–, H⁺,NH₄ ⁺); 0.2 m and 5.0 m (Cl^–) and 2.0–5.0 m(F^–). K⁺ and Na⁺ mirrored the SO₄ ^2– size-resolvedconcentrations closely, suggesting that these were transported primarily asK₂SO₄ and Na₂SO₄ in acidic solution, while Mg²⁺ andCa²⁺ presented modes in both <1 m and >1 m particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO₄ ^2–, Cl^–, F^–,H⁺, Na⁺, K⁺ and Mg²⁺ were observed around the 10 m particle diameter in this dust. The volcanic SO₄ ^2– flux leaving the craterwas 0.07 kg s^–1.     

Aircraft measurements of oxides of nitrogen along the eastern rim of the Asian continent: Winter observations

Aircraft observations of oxides of nitrogen (NO _y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO _y defined here is the sum of NO, NO₂, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:

1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO _y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
2. Over the Sea of Japan, tropospheric NO _y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
3. NO _y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO _y mixing ratio was about 200 pptv.

     

Measurements of Atmospheric Concentrations of Reduced Sulphur Compounds in the All Saints Bay Area in Bahia,Brazil

Atmospheric concentrations of several reduced sulphur compounds (H₂S, COS, CH₃SH, CH₃SCH₃, CS₂) originating from both natural and anthropogenic sources were measured at a number of locations in the All Saints Bay area and Reconcavo Baiano, Brazil.The volatile reduced sulphur compounds were collected by pre-concentration using cryo-tubes. Analysis of these compounds was carried out at a later date using gas chromatography with a flame photometric detector. In areas dominated by biogenic sources, the COS concentration varied between 0.5 and 1.0 ppbv, consistent with its normal global distribution in the atmosphere.Areas without direct industrial influence showed low atmospheric concentrations for all volatile sulphur compounds ( 0.25 ppb_v).The anthropogenic influence of the Petrochemical Complex in Camaçari resulted in relatively high levels of some reduced sulphur compounds, such as COS (8 ppb_v), CH₃SH (1.50 ppb_v), H₂S (1.35 ppb_v) and CS₂ (0.3 ppb_v). In mangrove areas, the H₂S concentrations (0.2 ppb_v) were almost twice as high as those in the air masses arriving from the Atlantic Ocean. The maximum H₂S concentrations were found in the industrial area of the Petrochemical Complex in Camaçari, but did not reach the limit of human perception (0.14 ppb_v) and rarely reached the typical recognizable smelling level (0.40 ppb_v). Industrial emissions from the Landulfo Alves Refinery increased the COS, DMS and CS₂ concentrations to 2.0, 0.55 and 0.2 ppb_v, respectively.     

A dual site study of the rainwater chemistry within the Western Pacific region

The two-year (1999–2000) rainwater chemistry at two monitoring sites in nearby coastal areas [Taiwan (TW) and Hong Kong (HK)] within the Western Pacific region has been studied. The volume weighted average pH values for the entire sampling period in TW and HK were 4.6 and 4.2, respectively. Sea salt Na⁺ and Cl⁻ were the most abundant species in the TW samples but and H⁺ were the most abundant in the HK samples. The sea salt and concentrations at TW were higher than those at HK both in the cold and warm seasons. Chloride depletion was minimal in the rainwater samples at both sites. Non seasalt- was associated with . Under the influence of the East Asian Winter Monsoon, the back-trajectory studies revealed that elevated anthropogenic species concentrations were associated with trajectories (1) very near to the continental boundary layer of Mainland China; or (2) along the coastline of Eastern China where large cities/industrial areas are located or (3) passing through the region of stagnant air over Northern/Eastern China. The lowest anthropogenic and crustal species concentrations measured in HK are associated with the summer monsoon and are attributed not only to the clean marine air masses but also to the relatively low SO₂, NO _x and NH₃ emissions from the South/ South East Asian countries, as well as infrequent biomass burning activities and wet scavenging at sources during the summer months. Approaching tropical cyclones led to the lowest pH values (4.2 in TW and 3.8 in HK) amongst the other weather categories. The findings here have been compared with other studies within East Asia and elsewhere.     

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.