Laboratory studies of some environmental variables controlling sulfur emissions from plants

Several trace sulfur gases that can have a significant influence on atmospheric chemistry are emitted from biological systems. In order to begin to address biological questions on the mechnisms of production of such gases, laboratory-scale experiments have been developed that reproduce such emissions under controlled conditions. Using a flux chamber technique, flats containing soil, or soil plus plants were sampled for the net fluxes of sulfur gases. The major sulfur gas emitted from all the plants tested (corn, alfalfa, and wheat) was dimethyl sulfide (DMS). Alfalfa and wheat also emitted lesser amounts of methanethiol, variable amounls of hydrogen sulfide, and in some experiments wheat emitted carbon disulfide. The use of a plant incubator allowed a systematic study of the effects of variables such as temperature, photon flux, and carbon dioxide levels, on these emissions. Fluxes of all the emitted sulfur gases increased exponentially with increasing air temperature, and increased with increasing photon flux up to a saturation level of \~300 E/m^–2 sec^-1. Three to four-fold changes in DMS flux were observed during light to dark or dark to light transitions. By varying the CO₂ content of the chamber flush gas, it was shown that the observed sulfur fluxes from corn and alfalfa were not related to the CO₂ concentration. Growing these crop plants through holes in a Teflon soil-covering film allowed a separate determination of soil and foliage emissions and substantiation of the light dependent uptake of COS by growing vegetation observed in previous field studies.     

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ²–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m³ (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m³, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m³, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m²/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m²/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m²/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m³, n=35) and Bering Sea (1.17 ± 0.87 nmole/m³, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m³, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO₄ ²– concentrations were higher near the continent. This suggests that nss-SO₄ ²– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO₄ ²– was similar to that of Rn-222 used as a tracer of continental air masses.     

Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l^-1 and from 1.4 to 11.3 nmol m^-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m^-2 d^-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m^-2 d^-1, respectively.     

Methane emission measurements in urban areas in Eastern Germany

We have investigated methane emissions from urban sources in the former East Germany using innovative measurement techniques including a mobile real-time methane instrument and tracer release experiments. Anthropogenic and biogenic sources were studied with the emphasis on methane emissions from gas system sources, including urban distribution facilities and a production plant. Methane fluxes from pressure regulating stations ranged from 0.006 to 24. l/min. Emissions from diffuse sources in urban areas were also measured with concentration maps and whole city flux experiments. The area fluxes of the two towns studied were 0.37 and 1.9 g/m²/s. The emissions from individual gas system stations and total town emissions of this study are comparable to results of similar sites examined in the United States.     

Spatial, Temporal and Interannual Variability of Methanesulfonate and Non-Sea-Salt Sulfate in Rainwater in the Southern Indian Ocean (Amsterdam, Crozet and Kerguelen Islands)

Methanesulfonate (MS^–) and non-sea-salt sulfate (nss-SO ₄ ^2– ), two of the major oxidation products of atmospheric dimethylsulfide (DMS), have been continuously measured in rainwater at three remote islands in the Southern Indian Ocean: Amsterdam since 1991, Crozet since 1992, and Kerguelen since 1993. The annual volume weighted mean (VWM) concentrations of nss-SO ₄ ^2– in rainwater were 3.19, 3.04 and 4.57 eq l^–1 at Amsterdam, Crozet, and Kerguelen, respectively while the VWM of MS^– were 0.24, 0.15 and 0.30 eq l^–1, respectively. At all three islands, MS^– presented a well-distinguished seasonal variation with a maximum during summer whereas the seasonal variation of nss-SO ₄ ^2– was less pronounced, possibly due to the increased anthropogenic influence during the winter period. Furthermore, MS^– presented significant interannual variations, in particular at Amsterdam and Crozet, which is closely related to the sea-surface temperature (SST) anomalies). Finally, the nss-SO ₄ ^2– deposition at Crozet Island presented a decreasing interannual trend, reflecting probably reductions in sulfur emissions from Southern Africa. On the contrary no interannual tendency was observed in the nss-SO ₄ ^2– concentrations at Amsterdam Island, indicating that the biogeochemical sulfur cycle at this area is mainly influenced by biogenic emissions.     

Precipitation Chemistry in the Sahelian Savanna of Niger, Africa

Within the framework of the IDAF (IGAC DEBITS AFRICA) network, we present in this paper data on precipitation and aerosol chemistry in the semiarid savanna of the Sahelian region of Niger. An automatic wet-only precipitation collector was operated at the Banizoumbou station during the entire 1996 rainy season (June to September 1996). Inorganic (Na⁺, NH ₄ ⁺ , K⁺, Mg²⁺, Ca²⁺, Cl^-, NO ₃ ^- , SO ₄ ^2- ) and organic contents of the precipitation (HCOOH, CH₃COOH, C₂H₅COOH) were determined by Ion Chromatography (IC) in 29 rainfall events. Once per week, bulk particle samples were collected on the same site, and soluble water material was determined by IC. We examined the influence of atmospheric gas and particle sources on the precipitation and aerosol chemical contents. We established the influence of marine, terrigenous, and biogenic sources in the Sahelian region. The terrigenous signature is dominant and related to Sahelian soil erosion, with a high calcium content in precipitation (31.2 eq L^-1) and in aerosols (1.8 g m^-3). Two other signatures of atmospheric sources are highlighted by the relatively high nitrogenous (ammonium and nitrate) and organic contents (formate, acetate) in the precipitation. Ammonium (12.9 eq L^-1) and nitrate (12.3 eq L^-1) contents confirm respectively the biogenic source of ammonia released by domestic animal excreta in Niger and the natural emissions from semiarid savannas soils, perturbed by wild or domestic animal grazing. In spite of a high potential acidity given by nitrate, formate and acetate; a weak acidity (H⁺ (2.1 eq L^-1) is calculated from the mean pH of 5.67 measured. A statistical analysis of the aerosol chemical composition clearly indicates that nitrates are strongly correlated at the 1% level with terrigenous ions, i.e., Ca²⁺ and Mg²⁺ (0.95 < r < 1). We observed a similar relationship between all the terrigenous ions and nitrate in the precipitation. In the Sahelian region, alkaline soil dust representative of the terrigenous contribution interact, with gaseous nitrogenous and carbonaceous compounds, leading to the neutralization of acid gases and subsequent weak acidity in precipitation. Finally, taking into account the main chemical characteristics of Banizoumbou precipitations and aerosols, which demonstrate the importance of heterogeneous and multiphase chemical processes, we propose a conceptual model of the atmospheric chemistry in the Sahelian region.     

Rainwater Chemistry and Wet Deposition over the Equatorial Forested Ecosystem of Zoétélé (Cameroon)

Within the framework of IDAF (IGAC DEBITS AFRICA: International GlobalAtmospheric Chemistry/DEposition of Biogeochemically Important TraceSpecies/Africa) network, data analysis is realised on precipitation chemical composition collected in Zoétélé, in Southern Cameroon. This station, located atabout 200 km from the Atlantic Ocean, is representative of a so-called `Evergreen Equatorial Forest' ecosystem. An automatic wet-only precipitation collector was operated at the station from 1996 to 2000. The rainfall regime, associated with eastward advection of moist and cool monsoon air masses, amounts to an average of 1700 mm/year. Inorganic and organic content of the precipitation were determined by IC in 234 rainfall events, representing a total 4,583 mm of rainfall from an overall of 7,100 mm.The mean annual precipitation chemistry and wet deposition fluxes characteristic of an African equatorial forest are quantified. Typical atmospheric gases and particles sources influence the precipitation chemical content and the associated deposition of chemical species. Indeed, hydrogen concentration is the highest (12.0 eq.L^–1) of the IDAF measurements, leading to acid rains with a low mean pH 4.92. The mineral species are dominated by nitrogenous compounds (NH₄ ⁺:10.5 and NO₃ ^–: 6.9 eq.L^–1), Ca²⁺ (8.9 eq.L^–1) and SO₄ ^{2 –} 5.1 eq.L^–1. Relationship between Ca^{2 +} and SO₄ ^{2 –} indicated aterrigeneous particulate source and an additional SO₄ ^{2 –} contributionprobably due to swamps and volcano emissions. Na⁺ and Cl^–concentrations, around 4.0 eq.L^–1, seem very low for this site,accounting for the marine source. Besides, strong correlations between NH₄ ⁺/K⁺/Cl^– indicate the biomass burning originof these species. Accordingly, precipitation chemistry in Zoétéléis influenced by three major sources: biogenic emissions from soil and forest ecosystems, biomass burning from savannah, and terrigenous signature from particles emissions of arid zones; and three minor sources: marine, volcano and anthropogenic. In spite of the relatively low concentration of all these elements, the wet deposition is quite significant due to the high precipitation levels, with for example a nitrogenous compounds deposition of 34 mmol.m^–2.yr^–1.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

Comparison Between Eddy-Correlation and Inertial Dissipation Methods in the Marine Atmospheric Surface Layer

A comparison of momentum fluxes determined by the eddy-correlation method(ECM) and the inertial dissipation method (IDM) has been performed using longterm measurements over the sea. The measurements were made on the island ofÖstergarnsholm in the middle of the Baltic Sea. The results show that a`classical' form of the inertial dissipation method, i.e., assuming that the transportterms are negligible, and using an effective value for the Kolmogorov constant of0.55, can be used with a mean relative difference between the two methods of about15% for -1 < z/L < 0.5 (z being height and L the Obukhov length). The IDMmethod works best for high wind speeds and neutral conditions. For low windspeeds (U < 6 m s^-1) the relation between the two methods is morecomplex. IDM then gives higher values than ECM on the average (about 20%),especially for swell conditions, indicating the need for an imbalance function inthe turbulent kinetic energy budget. Calculations of the effective Kolmogorovconstant, _a, suggest a dependence upon the wave age, _a increasing with increasing wave age, where the value 0.59 fits the data well for saturated waves.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time

A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO₂) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO₂/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO₄ ^2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.     

Fluxes of gases and particles above a deciduous forest in wintertime

Eddy-correlation measurements of the vertical fluxes of ozone, carbon dioxide, fine particles with diameter near 0.1 m, and particulate sulfur, as well as of momentum, heat and water vapor, have been taken above a tall leafless deciduous forest in wintertime. During the experimental period of one week, ozone deposition velocities varied from about 0.1 cm s^–1 at night to more than 0.4 cm s^-1 during the daytime, with the largest variations associated primarily with changes in solar irradiation. Most of the ozone removal took place in the upper canopy. Carbon dioxide fluxes were directed upward due to respiration and exhibited a strong dependence on air temperature and solar heating. The fluxes were approximately zero at air temperatures less than 5 °C and approached 0.8 mg m^–2 s^–1 when temperatures exceeded 15 °C during the daytime. Fine-particle deposition rates were large at times, with deposition velocities near 0.8 cm s^–1 when turbulence levels were high, but fluxes directed upward were found above the canopy when the surface beneath was covered with snow. Diffusional processes seemed to dominate fine-particle transfer across quasilaminar layers and subsequent deposition to the upper canopy. Deposition velocities for particulate sulfur were highly variable and averaged to a value small in magnitude as compared to similar measurements taken previously over a pine forest in summer.     

Spatial and temporal variations of methanesulfonic acid and non sea salt sulfate in Antarctic ice

A simultaneous glaciochemical study of methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^-) has been conducted on the Antarctic plateau (South Pole, Vostok) and in more coastal regions. The objective was to investigate marine sulfur emissions in very remote areas. Firstly, our data suggest that MSA and nss-SO₄ present in antarctic ice are mainly marine in origin and that DMS emissions have been significantly modulated by short term (eg. El Nino Southern Oscillation events) as well as long term climatic changes in the past. Secondly, our study of spatial variations of these two sulfur species seems to indicate that the atmosphere of coastal antarctic regions are mainly supplied by local DMS emissions whereas the atmosphere of the high plateau is also influenced by DMS emissions from more temperate marine latitudes. Thirdly, our study of the partitioning between MSA and nss-SO₄ suggest that the temperature could have been an important parameter controlling the final composition of the high southern latitude atmosphere over the last climatic cycle; colder temperature favoring the formation of MSA. However, our data also support a possible role played by changes in the transport pattern of marine air to the high antarctic plateau.     

Sulfur emissions to the atmosphere from natural sourees

Emissions of sulfur gases from both natural and anthropogenic sources strongly influence the chemistry of the atmosphere. To assess the relative importance of these sources we have combined the measurements of sulfur gases and fluxes during the past decade to create a global emission inventory. The inventory, which is divided into 12 latitude belts, takes into account the seasonal dependence of sulfur emissions from biogenic sources. The total emissions of sulfur gases from natural sources are approximately 0.79 Tmol S/a. These emissions are 16% of the total sulfur emissions in the Northern Hemisphere and 58% in the Southern Hemisphere. The inventory clearly shows the impact of anthropogenic sulfur emissions in the region between 35° and 50°N.     

Seasonal Variation in Amount and Composition of Monoterpenes Emitted by Young Pinus pinea Trees – Implications for Emission Modeling

Current inventories of terpenes released from vegetation consider only the short-term influences of light and temperature on emissions to simulate temporal variation during the year. We studied whole canopy emissions from young Pinus pinea during a 15-month enclosure in greenhouse chambers and examined data for other long-term influences. Mean daytime emission rates strongly increased during spring, reached an annual maximum of 200 pmol m^–2 total needle area s^–1 (1.1 g g^–1 leaf dry weight h^–1) between mid June and mid August, strongly declined in fall and reached an annual minimum of 1 pmol m^–2 s^–1 (0.006 g g^–1 h^–1) between January and February. Normalization to standard temperature and light conditions did not change the annual time course of emissions, but reduced summer to winter ratio from a factor of 200 to about 45. Seasonal variation was characterized also by changes in terpene composition: among the six main compounds, three (t--ocimene, linalool, 1.8-cineol) were exclusively emitted during sunlit hours in the main vegetation period, whereas the other (limonene, -pinene, myrcene) were emitted day and night and throughout the seasons. The results suggest that different terpene sources in P. pinea foliage exist and that a great part of the annual emission course observed here results from seasonal influences on these sources. A global model to simulate plant emissions is proposed, which accounts for seasonal influences on emissions in addition to the short-term effects of temperature and light. The model is tested on field data and discussed for its general application.     

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.