Atmospheric aerosol measurements over North America and the North Atlantic Ocean

Measurements of atmospheric aerosol, obtained during thirty-nine transit flights within North America and across the North Atlantic Ocean, are presented and analyzed. The measurements comprise Aitken nucleus concentrations, particle size distributions, and the particle component of the light-scattering coefficient. Measurements of ozone are also presented.These data provide information on the ‘background’ and average values of the atmospheric aerosol in the lower and middle troposphere in continental, marine and high-latitude airmasses. The effects of temperature inversions, vertical mixing, clouds and precipitation, and stratospheric intrusions are illustrated. Time and spatial scales are derived for the transformations of the aerosol from those characteristic of a marine airmass into those characteristic of a continental airmass and vice versa.     

Meteorological effects on smoke and sulphur dioxide concentrations in the Manchester area

Observations of mean daily concentrations of smoke and of sulphur dioxide, obtained from several National Survey sites in the Manchester area, have been correlated with meteorological data and with certain other variables. Two periods have been examined, one from May 1975 to March 1977, the other from October 1978 to April 1979; the second, shorter period was more closely analysed. The model adopted for analysis differed from the power-law form selected by most previous investigators; it appears physically more satisfactory and in practice gave better correlation with sulphur dioxide observations. For the long period, the relatively crude analysis explained about two-thirds of the variance: for the shorter period, using more detailed meteorological data, the proportion explained ranged from 72 to 93 %.     

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m⁻³ in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr⁻¹, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.     

Marine sulfur cycling and the atmospheric aerosol over the springtime North Atlantic

We investigated the distribution of phytoplankton species and the associated dimethyl sulfur species, dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) on a cruise into the spring bloom region of the northern North Atlantic (near 47 degrees N, 19 degrees W). The cruise was timed to characterize the relationship between plankton dynamics and sulfur species production during the spring plankton bloom period. At the same time, we measured the DMS concentrations in the atmospheric boundary layer and determined the abundance and composition of the atmospheric aerosol.The water column studies showed that the interplay of wind-driven mixing and stratification due to solar heating controlled the evolution of the plankton population, and consequently the abundance of particulate and dissolved DMSP and DMS. The sea-to-air transfer of DMS was modulated by strong variations in wind speed, and was found to be consistent with currently available transfer parameterizations. The atmospheric concentration of DMS was strongly dependent on the sea surface emission, the depth of the atmospheric boundary layer and the rate of photooxidation as inferred from UV irradiance. Sea-salt and anthropogenic sulfate were the most abundant components of the atmospheric aerosol. On two days, a strong dust episode was observed bringing mineral dust aerosol from the Sahara desert to our northerly study region. The background concentrations of marine biogenic sulfate aerosol were low, near 30-60 ppt. These values were consistent with the rate of sulfate production estimated from the abundance of DMS in the marine boundary layer.     

A multi-component data assimilation experiment directed to sulphur dioxide and sulphate over Europe

Fine particulate matter (PM) is relevant for human health and its components are associated with climate effects. The performance of chemistry transport models for PM, its components and precursor gases is relatively poor. The use of these models to assess the state of the atmosphere can be strengthened using data assimilation. This study focuses on simultaneous assimilation of sulphate and its precursor gas sulphur dioxide into the regional chemistry transport model LOTOS–EUROS using an ensemble Kalman filter. The process of going from a single component setup for SO₂ or SO₄ to an experiment in which both components are assimilated simultaneously is illustrated. In these experiments, solely emissions, or a combination of emissions and the conversion rates between SO₂ and SO₄ were considered uncertain. In general, the use of sequential data assimilation for the estimation of the sulphur dioxide and sulphate distribution over Europe is shown to be beneficial. However, the single component experiments gave contradicting results in direction in which the emissions are adjusted by the filter showing the limitations of such applications. The estimates of the pollutant concentrations in a multi-component assimilation have found to be more realistic. We discuss the behavior of the assimilation system for this application. The model uncertainty definition is shown to be a critical parameter. The increased complexity associated with the simultaneous assimilation of strongly related species requires a very careful specification of the experiment, which will be the main challenge in the future data assimilation applications.     

Understanding the contributions of anthropogenic and biogenic sources to CO enhancements and outflow observed over North America and the western Atlantic Ocean by TES and MOPITT

We investigate the effects of anthropogenic and biogenic sources on tropospheric CO enhancements and outflow over North America and the Atlantic during July–August 2006, the 3rd warmest summer on record. The analysis is performed using the 3D Regional chEmical trAnsport Model (REAM), satellite data from TES on the Aura satellite, MOPITT on the Terra satellite and surface monitor data from the SEARCH network. The satellite measurements of CO provide insight into the location of regional CO enhancements along with the ability to resolve vertical features. Satellite and surface monitor data are used to compare with REAM, illustrating model's ability to reproduce observed CO concentrations. The REAM model used in this study features CO emissions reduced by 50% from the 1999 EPA NEI and biogenic VOC emissions scaled by EPA-observed isoprene concentrations (20% reduction). The REAM simulations show large variations in surface CO, lower tropospheric CO and column CO, which are also observed by the surface observations and satellite data. Over the US, during July–August 2006, the model estimates monthly CO production from anthropogenic sources (5.3 and 5.1 Tg CO) is generally larger than biogenic sources (4.3 and 3.5 Tg CO). However, the model shows that for very warm days, biogenic sources produce as much CO as anthropogenic sources, a result of increased biogenic production due to warmer temperatures. The satellite data show CO outflow occurs along the East Coast of the US and Canada in July and is more broadly distributed over the Atlantic in August. REAM results show the longitudinally exported CO enhancements from anthropogenic sources (3.3 and 3.9 Tg CO) are larger than biogenic sources (2.8 and 2.7 Tg CO) along the eastern boundary of REAM for July–August 2006. We show that when compared with the impacts of both sources on increasing tropospheric CO exports, the relative impacts in August are greater than in July because of preferable outflow transport.     

Spectrophotometric determination of sulphur dioxide

Sulphur dioxide, an important industrial gas and air pollutant, is usually estimated using mercury salts. The authors have developed a method in which hazardous mercury salts are avoided. Sulphur dioxide is trapped in aqueous morpholine and mixed with the excess of dichromate solution in acidic medium. The hexavalent chromium in dichromate is reduced to trivalent chromium by sulphur dioxide and the excess of hexavalent chromium is determined with diphenylcarbazide which yields a soluble red-violet complex with an absorption maximum at 540 nm. The decrease in the absorbance values of the red-violet complex formed after reduction, when compared to that of a reagent control, is proportional to the concentration of sulphur dioxide used for reduction. Beer's law operates between 0.4 and 4 microg ml(-1) concentration of sulphur dioxide in solution.     

Measurements of nitrogen dioxide and sulphur dioxide concentrations in urban and rural areas of Poland using a passive sampling method

Measurements of 1-month concentrations of NO(2) and SO(2) were carried out in the period from May 1993 to April 1994 in 147 points in 30 major cities of Poland and in 31 points in rural areas. The measurement points were divided into five classes representing: centres of cities, residential areas, industrial areas, traffic locations and rural areas. Passive samplers were prepared in one laboratory, mailed to local laboratories for sampling and then returned for analysis. The same samplers were used for collecting both NO(2) and SO(2). Analyses for NO(2) absorbed as nitrite were made spectrophotometrically after reaction with Saltzman reagent. Sulphur dioxide was determined as sulphate with ion chromatography. The consistency of data allowed comparison of levels of air pollution in different cities and the production of maps of spatial distribution of NO(2) and SO(2) in rural areas of Poland.     

Long-term mean concentrations of atmospheric smoke and sulphur dioxide in country areas of England and Wales

The representiveness of daily observations at atmospheric smoke and sulphur dioxide concentrations monitored at National Survey country sites is discussed. Long-term mean smoke and sulphur dioxide concentrations for wind octants at 21 country sites in England and Wales are presented and examined in the context of urban and background concentrations. Sources are identified and the effects of wind speed on the long-distance transport of air pollution discussed.Estimates of domestic and industrial smoke emissions, by counties, for England and Wales are given. An expression is developed from which long-term concentrations of smoke or sulphur dioxide at a country site can be calculated.     

Emissions of biogenic sulphur compounds from several wetland soils in Florida

Emission rates of the biogenic sulphur gases hydrogen sulphide, dimethyl sulphide, carbon disulphide and dimethyl disulphide have been measured from the exposed soils of five wetland plant communities in Florida. Dimethyl sulphide and hydrogen sulphide were the predominant species emitted. All the studied ecosystems showed diel variation in the emission rates of the biogenic sulphur gases with the highest emissions rates occurring early- to mid-afternoon, and the lowest emission rates occurring during the early morning. The relative magnitude of emissions from the individual ecosystems followed the trend Distichlis spicata >Avicennia germinans >Batis maritima ≅ Juncus roemerianus ≅ Cladium jamaicense. Only the emission rates from the peaty D. spicata site are comparable in magnitude to previous emission measurements in wetland ecosystems of Spartina alterniflora and associated mud flats.     

Foliar responses of five plant species to ozone and a sulphur dioxide/ozone mixture after a sulphur dioxide pre-exposure

Plants that were pretreated with 0.15 ppm SO₂ for either 2 or 3 d before an intermittent O₃ or SO₂/O₃ exposure exhibited differences in per cent visible foliar injury that often varied significantly from plants that received no SO₂ pretreatment. Differences that were observed could not be explained on the basis of leaf diffusive resistance alone. The SO₂ pretreatment for 2 d caused a decrease in visible O₃ injury in white bean, an increase in visible O₃ injury in cucumber and radish, and had no effect on soybean and tomato. The same pretreatment caused an increase in visible injury from the SO₂/O₃ mixture in white bean, a decrease in visible injury for cucumber and tomato, and had no effect on soybean and radish. However, these same trends did not occur when the SO₂ pretreatment was increased to 3 d. Pretreatment with sub-acute levels of SO₂ can significantly alter a plant's response to O₃ or a mixture of SO₂/O₃, the change in response being sensitive to the pretreatment SO₂ dosage. The nature of the visible injury symptoms from O₃ or the pollutant mixture were not altered for any of the plant species regardless of the length of time of the SO₂ pretreatment and, generally, the onset of visible injury was not greatly altered.     

Factors affecting the collection of sulphur dioxide from low-velocity jets

Some factors affecting the collection efficiency of the low-velocity jet impinger and conductivity cell have been investigated for low concentrations of sulphur dioxide in air.These factors were : (1) the size of the conductivity cell ; (2) the bore of the jet ; (3) the air flow rate ; (4) the distance between the jet and the reagent surface; (5) the ambient temperature.By choosing optimum values for factors 1–4, a collection efficiency of approximately 90% may be obtained at room temperature.     

The oxidation of sulphur dioxide in electrolyte droplets

The rate of absorption of sulphur dioxide into deliquescent aerosols of MgCl₂, NaCl and (NH₄)₂SO₄ has been studied using a radioactive tracing technique. The amount of SO₂ absorbed was approximately linear in the calculated liquid water content of the aerosols and reached about 12 mg g⁻¹ water after a reaction time of 145 min. Over the range 1–20 ppm the reaction was zero order in gas phase SO₂ concentration. Additional metal catalysts (Mn²⁺, Fe³⁺) had relatively small effects on the oxidation rates whilst NO²⁺ (0–20 ppm) had a large effect on the initial rate but did not significantly increase the final amount of SO₂ absorbed. The rates of reaction are shown to be far higher than in pure water and significant reaction continues down to pH 1–2. A detailed model of ionic activities and equilibria in the droplets is developed to aid the interpretation of the results and the implications for natural aerosols such as sea salt assessed.