Characteristics of SO2, NO2, Soot and Benzo(a)Pyrene Concentration Variation on the Eastern Coast of the Baltic Sea

The investigation of SO₂, NO₂, soot and benzo(a)pyrene (BP) has been performed at the background station on the eastern coast of the Baltic Sea since 1980. A significant decreasing trend has been observed for SO₂ and NO₂, while soot and BP concentrations were changing insignificantly. The decreasing SO₂ and NO₂ high concentrations (>10µg·m^?3) have been determined in the air masses coming from the Western and Central Europe to Lithuania since 1900. The concentration of SO₂ in a range of 0–5µg·m^?3 and the concentration of NO₂ in a range of 0–10µg·m^?3 are characteric of the background atmospheric air.     

Throughfall Chemistry in a Sitka Spruce Plantation in Response to Six Different Simulated Polluted Mist Treatments

A mixed provenance Sitka spruce plantation, planted in 1986 on a drained deep peat, has been exposed to 6 different simulated mist treatments in 4 replicated blocks since 1996. Treatments provided N and/or S at a concentration of 1.6 mol m^?3, supplying ca. 50 kg S and/or N ha^?1 yr^?1 as N (NH₄NO₃), S (Na₂SO₄), NS Acid (NH₄NO₃ + H₂SO₄ at pH 2.5), 2NS Acid (double dose by application at twice frequency), a control treatment supplied with additional rainwater only and a 'no treatment' set of plots. Throughfall, preserved with thymol in the field, was collected using gutters with a surface area of 1 m² in all the replicate plots, and was analysed for all major ions. Prior to treatment in 1999, S deposition in throughfall exceeded that in rain because of dry deposition of SO₂ and SO₄ ^2? to the canopy; NH₄ ⁺ and NO₃ ^? ions were both retained in the canopy. During treatment, only 20–40% of the applied N in the high-N treatments was retained in the canopy. Acidity in the applied mist was partly neutralised by the canopy, but not primarily through exchange of base cations, leading to the conclusion that weak organic acids, in solution or in situ in the canopy, contributed to the buffering of the H⁺ ion deposition in the acid treatments.     

Throughfall deposition of ammonium and sulphate during ammonia fumigation of a scots pine forest

The estimation of the dry deposition of sulphur dioxide to forests is confounded by the possibility of co-deposition of SO₂ with NH₃ on leaf surfaces. A sector of Scots pine forest was selectively fumigated with NH₃ to give average concentrations up to 15 ppbV (nL L^–1) above ambient, in order to test the hypothesis that increased air concentrations of NH₃ would enhance the dry deposition of SO₂, and the consequent amounts of SO₄ ^2– measured in throughfall below the forest canopy. Ammonia gas, generated by evaporation of concentrated aqueous solution, was released above the canopy in proportion to wind speed when the wind direction was between south and west. Concentrations of NH₃ at canopy height were measured using passive diffusion tubes; throughfall was preserved with thymol and measured weekly. Meteorological data and SO₂ concentrations were recorded continuously, to permit the estimation of dry deposition input. Deposition of NH₄ ⁺ in throughfall over 8 months was increased by up to 40 meq m^–2 relative to control sites upwind of the NH₃ release point, with largest values closest to the release point. Deposition of SO₄ ^2– in throughfall was also enhanced in the fumigated area, by up to 20 meq m^–2, even though average ambient SO₂ concentrations were 2.3 ppbV. The results are discussed in terms of the factors controlling SO₂ deposition on forest surfaces, the development of appropriate deposition models, and their relevance to using throughfall as an estimate of total S deposition.     

Inorganic and organic sulfur profiles in nine Sphagnum peat bogs in the United States and Czechoslovakia

Depth profiles of total S, organic S, soluble SO ₄ ^2? -S, FeS, and FeS₂ were characterized for Sphagnum-derived peat cores collected from 9 sites. Marcell S-2 Bog (MN), Tamarack Swamp (PA), Cranesville Swamp (MD/WV), and Big Run Bog (WV) receive water from precipitation and upland runoff; atmospheric S deposition is 13, 47, 54, and 114 mmol m^?2, yr^?1, respectively. McDonald's Branch Swamp (NJ) is predominantly groundwater fed. Tub Run Bog (WV) and Allegheny Mining Bog (MD) receive augmented SO ₄ ^2? inputs through acid coal mine drainage. Jezerní slat' and Bo?í Dar Bog in Czechoslovakia receive atmospheric S inputs of 33 and 243 mmol m^?2 yr^?1, respectively. In the peat from all sites except Allegheny Mining Bog, where the substantially augmented SO ₄ ^2? input was reflected in an unusually high dissolved SO ₄ ^2? pool in the surface peat, organic S (probably mostly carbon bonded S) was the dominant S fraction; FeS₂ was generally the dominant inorganic S fraction. Subsurface peaks in total S, organic S and FeS₂-S in peat from the runoff water fed sites were interpreted as indicative of depth-dependent patterns in S reduction/oxidation and in S immobilization/mineralization. Unless SO ₄ ^2? inputs to a site are tremendously augmented (e.g., Allegheny Mining Bog), the rapid turnover of the dissolved SO ₄ ^2? pool combined with the relative stability of the other inorganic and organic S pools, apparently functions as an effective buffer against site differences in S inputs, leading to a general similarity in vertical S profiles in the peat deposits.     

Microbial S-oxidation in soils exposed to heavy atmospheric pollution

Soils exposed to atmospheric pollution (> 125 SO₂μg m^?3). contained significantly greater numbers of thiobacilli and sulphur-oxidizing fungi than did similar but unpolluted soils. S-Oxidizing heterotrophic bacteria and actinomycetes were, however, infrequently isolated from either polluted or unpolluted soils. Polluted soils contained more fungi (total count) than unpolluted soils but contained fewer heterotrophic bacteria (total count).The distribution of S-oxidizing micro-organisms was closely associated in polluted soils with total S, S₂O^2?₃, S₄O³ amd SO^2?₄ concentrations. These ions increased in concentration below the canopy of polluted sycamore, while soil pH was lower.Rhodanese activity was higher in polluted than in unpolluted soils. The results indicate that microbial S-oxidation is actively occurring in soils exposed to heavy atmospheric pollution.     

Formation and Deposition of Ozone in a Red Pine Forest

Concentrations of ozone and nitrogen oxides, together with air temperature and solar radiation intensity, were measured at several heights on a tower standing through the canopy of a red pine forest in summer and in autumn. In the summer observation, the diurnal variation patterns of ozone concentration both above and below the canopy were all similar and parallel to the solar radiation intensity. Using the data collected immediately above the canopy, deviation from the Leighton relationship and variations of concentration sums [O₃] + [NO] and [NO₂] + [NO] were examined, and as a result, it was supposedthat ozone was photochemically formed there in the daytime, probably because hydrocarbons emitted from pine trees broke the photostationary state among ozone and nitrogen oxides. The vertical temperature profile exhibited an inversion at the leaf-layer, which must have hindered vertical mixing of the air and made the trunk space more or less isolated from the upper atmosphere. These observations led to an idea that the similarity of the ozone variation pattern at every height was caused by the photochemical formation that proceeded simultaneously above and below the canopy rather than by vertical transport. Such situations of ozone formation were supported by observation of two maximums in the ozone vertical profile, one immediately above the canopy and another in the trunk space. Another feature of the ozone profile was a deep minimum in the leaf layer, which indicated ozone deposition onto leaf surfaces. This study thus revealed concurrence of ozone formation and deposition, and left two potentially important implications worthy of further investigation: (1) a forest is not always a sink but can be a source of ozone in sunlit conditions, and (2) deposition of ozone to trees can take place not only from outside but also from inside of a forest. In the autumn observation, however, the ozone formation was barely recognizable above the canopy and no longer found in the trunk space; in addition, the ozone concentration minimum in the leaf layer disappeared, suggesting that the deposition or removal was dependent on temperature.     

NITROGEN–PHOSPHORUS–POTASSIUM EFFECTS ON FORMS OF SULFUR IN LEAVES AND FRUITS OF CUCUMBER

ABSTRACT

The impact that nitrogen (N), phosphorus (P), and potassium (K) application rates on the sulfur (S) fractions in leaves and fruits of greenhouse-grown cucumbers plants (Cucumis sativus L. cv. Brunex) are presented. The treatments were as follows: N (N1=5 g NO₃NH₄/m², N2=10 g NO₃NH₄/m², N3=20 g NO₃NH₄/m², N4=40 g NO₃NH₄/m²), two levels of P (P1=8 g H₃PO₄/m² and P2=16 g H₃PO₄/m²), and two levels of K (K1=20 g K₂SO₄/m² and K2=40 g K₂SO₄/m²). The foliar and fruit contents were determined for total S, organic S and sulfate. The influence of the N treatments on the total S (St: organic S +sulfate) concentration, proved significant, showing a progressive increase in the leaf and fruit concentrations. In the leaves, the P slightly diminished the St concentration but values in the fruits did not appreciably differ from control. The K dosage did not cause the St concentration to differ from that of P, although in the fruit a slightly lower St concentration appeared in the K2 treatment. The response of the organic-S concentration in the leaves resembled that of St, and thus organic S should not be used as a diagnostic method for S status. In the relationship SO₄ ^2-/St, the SO₄ ^2- concentration proved more influential than did the St form, providing a more accurate representation of the potential status of this nutrient in the plant.     

Gaseous Emissions During the Coal Mining Activity and Neutralizing Capacity of Ammonium

This paper presents the simultaneous measurement of atmospheric concentration of gaseous NH₃, SO₂ and NO₂, and particulate NH ₄ ⁺ released from the mining activities of coal-mine area, Tirap colliery, Margherita (Assam). Gas samples were collected by impinger method and were analyzed colorimetrically. The vapor-phase concentration of NH₃, SO₂, and NO₂ range between 4.7?C40.03, 1.47?C6.14, and 1.92?C2.40???g/m³. The NH ₄ ⁺ concentration in PM₁₀ and PM_2.5 ranges between 0.02?C0.07 and 0.008?C0.03???g/m³, respectively. Moderately high concentrations of NH₃ and SO₂ on the first day were due to the coal-burning activity near the sampling site, while the low concentration of NO₂ is due to less vehicle density near the sampling point. All the observed concentrations are below than those reported for the urban areas and the prescribed limit fixed by National Ambient Air Quality Standard, India. Study indicates that ammonia is the major neutralizing agent for sulfate and nitrate ions present in the particulate matter during mining activities.     

Interactive effect between sulfate and selenate on glutathione pool in garden rocket (Eruca sativa L.) leaves

Garden rocket (Eruca sativa L.) plants grown in sand culture were irrigated with normal 1/10 Hoagland's medium [low sulfate (SO₄^2?)] or with double SO₄^2? concentration (high SO₄^2?), each supplemented with 0, 2, 10 ppm SeO₄^2? as sodium selenate for 30 days. Increasing SO₄^2? concentration in the nutrient medium diminished SeO₄^2? uptake, foliar hydrogen peroxide (H₂O₂), and MDA via enhancing the glutathione pool and their enzyme activities. These results showed that increasing SO₄^2?/SeO₄^2? ratio in nutrient medium of rocket plants played an important role in selenate detoxification.     

Lysimeter study with a cambic arenosol exposed to artificial acid rain: II. Input-output budgets and soil chemical properties

The effects of artificial precipitation with different pH levels on soil chemical properties and element flux were studied in a lysimeter experiment. Cambic Arenosol (Typic Udipsamment) in monolith lysimeters was treated for 6 1/2 yr with 125 mm yr^?1 artificial rain in addition to natural precipitation. Artificial acid rain was produced from groundwater with H₂SO₄ added. pH levels of 6.1, 4 and 3 were used. ‘Rain’ acidity was buffered, mainly due to cation exchange with Ca²⁺ and Mg²⁺, which were increasingly leached due to the acid input. The H⁺ retention was not accompanied by a similar increase in the output of Al ions, but a slight increase in the leaching of Al ions was observed in the most acidic treatment. The net flux of SO₄ ^2? from the lysimeters increased with increasing input of H₂SO₄, but in the most acidified lysimeters significant sorption of SO₄ ^2? was observed. The sorption was, however, most likely a concentration effect. The ‘long-term’ acidification effects on soil were mainly seen in the upper O and Ah-horizons, where an impoverishment of exchangeable Ca²⁺ and Mg²⁺ was observed. An increased proportion of Al ions on exchange sites in the organic layer was observed in the pH 3-treated soil. By means of budget calculations the annual release of base cations due to weathering was estimated to be between 33 and 77 mmol_c m^?2.     

The cation denudation rate as a quantitative index of sensitivity of eastern Canadian rivers to acidic atmospheric precipitation

A model has been developed that relates the cation denudation rate (CDR) of a watershed (the rate that cations derived from chemical weathering are carried off by runoff), the atmospheric load of excess SO₄, and the pH of the river. Chemical and discharge data for rivers in Nova Scotia and Newfoundland were used to develop and test the model, which is based upon the common major ion chemistry of soft surface waters, and may be expressed by three statements: (1) CDR (meq m^?2 yr^?1) ? Excess SO₄ ^?? load (meq m^?2 yr^?1) = HCO₃ ^? (meq m^?2 yr^?1), (2) HCO₃ ^? (meq m^?2 yr^?1)/Runoff (m³ m^?2 yr^?1) = HCO₃ ^? (meq m^?3), (3) pH = pK + \(pP_{CO_2 } \) ? pHCO₃ ^?. The model in concentration form applies well to lakes. A detailed analysis of the data for the Isle aux Morts River, Newfoundland, is presented, showing that the CDR varies throughout the year, affected by both discharge and seasonal pattern.     

Long-term (13 years) measurements of SO2 fluxes over a forest and their control by surface chemistry

Long-term fluxes of sulphur dioxide (SO₂) have been measured over a mixed suburban forest subjected to elevated SO₂ concentrations. The net exchange was shown to be highly dynamic with substantial periods of both upward and downward fluxes observed in excellent conditions for flux measurement. Upward fluxes constituted 30% of selected fluxes and appeared more frequently when the canopy was acidic. Upward fluxes were shown to be due to desorption from a drying surface or when ambient levels declined after periods of increased SO₂ exposure.The long term average SO₂ flux (F) was −59 ng SO₂ m⁻² s⁻¹ for the period 1997-2009 corresponding to an average SO₂ concentration of 12.3 μg SO₂ m⁻³ and a deposition velocity υ_d of 5 mm s⁻¹. The smallest deposition fluxes and υ_d were measured in dry conditions (−42 ng m⁻² s⁻¹ and 3.5 mm s⁻¹, resp.), which represented 57% of all cases. Wet canopies were more efficient sinks for SO₂ and a dew-wetted canopy had a smaller υ_d (6 mm s⁻¹) than a rain-wetted canopy (ca 10 mm s⁻¹). Seasonal variability reflected differences in chemical climate or canopy buffering properties. During the summer half-year when surface acidity was low due to higher NH₃/SO₂ ratios, a higher deposition efficiency (υ_d/υ_dmax) and lower non-stomatal resistance (R_w) were observed compared to winter conditions. Comparisons of R_c for different combinations of canopy wetness and surface acidity categories emphasized the importance of both factors in regulating the non-stomatal sinks of SO₂. Increased surface water acidity gradually led to a lower υ_d/υ_dmax and an increased R_c for all considered canopy wetness categories. The smallest υ_d/υ_dmax ratio and highest R_c were obtained for a dry canopy with high surface acidity. Conversely, a rain-wetted canopy was the most efficient sink for SO₂. The canopy sink strength was further enhanced by high friction velocities (u_*), optimizing the mechanical mixing into the canopy. Long-term trends were strongly coupled to changes in the NH₃/SO₂ ratio, which has clearly enhanced the deposition efficiency of SO₂ in recent years.     

Soil response to s and n treatments in a Northern New England low elevation coniferous forest

A field experiment was designed to evaluate the effects of differing forms of acidifying S and N compounds on the chemistry of soils and soil solutions in a low elevation coniferous forest in northern New England. Treatments consisted of O, 1500, 3000, and 6000 eq of SO₄ ^2? or NO₃ ^? ha^?1 for the 1987 growing season applied biweekly as H₂SO₄ or HNO₃, or in a single application as dry] (NH₄)₂SO₄. Acidifying treatments resulted in a significant increase in soil solution SO₄ ^2? (1.2 to 2.6) or NO₃ ^? (12 to 80) in the upper B horizon. Excess strong acid anion leaching was associated with an accelerated loss of base cations, particularly MG²⁺ As solutions passed through the upper 25 cm of the soil profile, mean SO₄ ^2? concentrations decreased by 5 to 50% of the initial values, indicating that much of the applied SO₄ ^2? was immobilized in the upper portion of the pedon. Elevated concentrations of adsorbed and water-soluble SO₄ ^2? indicate that abiotic adsorption of SO₄ ^2? by soils is the dominant mechanism for the initial attenuation of SO₄ ^2? concentrations in these solutions. Other soil properties showed only small or no change due to treatments over the single growing season of this study. These results indicate that H₂SO₄, HNO₃, and (NH₄)₂SO₄ can all effectively increase strong acid anion concentrations in the soil-soil solution system.     

Climate confounds detection of chemical trends related to acid deposition in upper Midwest lakes in the USA

Between 1983–94, as acid deposition rates declined, SO₄ ^2? concentrations decreased in 18 of 28 lakes monitored by the upper Midwest LTM program. The expected recovery of ANC and pH was less common, however. Differences in climate may account for divergent trend patterns across the region. Only in Minnesota, where climatic shifts were less pronounced, did we observe a general pattern of increasing lake ANC and pH accompanying declines in SO₄ ^2?. In contrast, the widespread negative trends in lake SO₄ ^2? in the upper Michigan lakes were generally not associated with recovery of ANC and pH, but with decreases in Ca+Mg. These cation decreases may be linked to decreased groundwater inputs during the drier climatic conditions characterizing the study period and decreases in Ca+Mg in atmospheric deposition. In many of the Wisconsin lakes, an overall decline in SO₄ ^2? was precluded by SO₄ ^2? increases during a 4-year drought midway through the study period. During the drought, declining lake water level and volume caused evaporative concentration of solutes, and may have decreased the areal extent of sulfate reduction. Despite controls on sulfur emissions across the region, recovery of pH and ANC has been hindered by climatic shifts and concurrent decreases in atmospheric deposition of cations.     

Mesoscale spatial variability of sulfate in air and rainwater at St. Louis

Sulfate concentrations in rainwater and in air measured on four summer days at St. Louis were highly variable, both spatially or temporally. Maximum/minimum ratios of aerosol SO _inf4 ^sup? varied by up to a factor of 9, and those in rainwater by a factor of 3 on the average. Generally, SO _inf4 ^sup? concentration patterns in air and rainwater were similar, and consistent with wind direction and the location of sources. Direct relationships between SO _inf4 ^sup? in air and in water were evident on two of the individual days, but not for all days together. The non-uniformity of the SO _inf4 ^sup? pattern plus consideration of possible sources of SO _inf4 ^sup? suggests that nucleation of SO _inf4 ^sup? particles must be a major cause of S scavenging, with some possible influence from sub-cloud impaction.     

Field studies of pine,spruce and aspen periodically subjected to sulfur gas emissions

Field studies of photosynthesis in Pinus contorta/Pinus banksiana (lodgepole pine/jack pine) hybrids, Picea glauca (white spruce) and Populus tremuloides (aspen) subjected to SO₂ and H₂S from a nearby natural gas processing plant were initiated near Whitecourt, Alberta, Canada during the summer of 1974. The site was characterized as a Pinus-Picea glauca/Arctostaphylos uva-ursi association (pine-white spruce/bearberry). A 15 m high scaffold was used as access to mid-crown foliage in the pines while the spruce and aspen were accessible from the round. Net assimilation rates, transpiration rates and leaf resistances were calculated and water deficits were monitored. Photosynthetic rates measured were in a low range for the conifers studied, with pine having a maximum of 3.28 mg dm^?2 h^?1 and white spruce a maximum value of 2.3 mg dm^?2 h^?1 The low maximum photosynthetic rate determined for aspen is thought to be attributable to the onset of autumn. Chemical analyses for SO₄-sulfur using the methylene blue colorimetric method of Johnson and Nishita (1952) showed levels of 300 to 700 ppm, with the older foliage showing slightly higher values. Visible chronic S02 symptoms had a pronounced sun, or upward, orientation. Ambient SOD H₂S and total S were measured using a Tracor 270HA Atmospheric Sulfur Analyzer (chromatographic method) and trends in ambient SO₂ concentrations using an Envirometrics SO₂ Analyzer (polarographic method). Concentration was found to be variable for SO₂ and generally below 0.05 ppm. A concentration gradient of SO₂ was found to exist in the lodgepole pine/jack pine stand with the SO₂ values above the canopy generally higher than below the canopy (0.1 ppm above and 0.05 ppm below). This condition was occasionally reversed. The plant canopy is considered to act as a barrier to downward diffusion of the S emissions in the first case and also a barrier to upward diffusion of S emissions present due to advection in the stand in the second case. The vegetative environment surrounding the Windfall Gas Plant is definitely affected by S gas emissions but the extent remains to be determined.     

Estimation of Dry Deposition by Using a Filter Pack Method at Chunchon, Korea

Atmospheric gases and particulates were collected using four-stage filter-pack in Chunchon from January through December in 1999. Particulate SO₄ ^2? and NO₃ ^?, and gaseous HNO₃, SO₂ and NH₃ were analyzed. Annual average concentration of SO₄ ^2?(S), NO₃ ^?(S), HNO₃ (g), SO₂(g) and NH₃(g) were 5.75µg/m³, 4.98µg/m³, 0.33ppb, 1.52ppb and 7.25ppb, respectively. Annual dry deposition fluxes were estimated using the measured concentration and dry deposition velocity published by other research group. Annual dry deposition of S was 287kg · (km)^?2·y^?1, which accounted for about 30% of total S deposition. For N deposition, dry deposition is predominant; about 70% of total N deposition was through dry process mostly as forms of NH₃ and HNO₃.     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

Measurements of wet and dry deposition in a Northern Hardwood forest

Inputs of wet and dry deposition were monitored at the Huntington Forest in the Adirondack Mountains of New York for two years in the open and beneath the canopy of a northern hardwood forest. In the open, ion flux estimates were similar using wet-only weekly (NADP protocol) and event collections, but bulk collections were higher for all ions except H⁺, which was much lower. These differences were due to the contribution of dry deposition and possible biotic alterations in bulk collectors. Dry deposition was estimated using air concentrations and ion-specific depositional velocities modeled with meteorological data, and contributed substantially to the input of all ions [H⁺ (45%), Na⁺ (24%), K⁺ (22%), NH₄ ⁺ (12%), Ca²⁺ (58%), Mg²⁺(43%), NO₃ ^? (55%), Cl^? (27%) and SO₄ ^?2 (26%)]. Dry input of base cations was dominated by coarse particles, whereas gaseous inputs were more important for S and NO₃ ^?. Atmospheric concentrations of SO₂ and inputs of SO₄ ^2? and H⁺ were lower at this site than sites closer to point sources of S gas emission. The importance of estimating atmospheric inputs was examined using examples of elemental budgets. For example, different estimates of the contribution of dry deposition of SO₄ ^2? (9–21 meq m^?2 y^?1) resulted in conclusions ranging from no net retention to a net loss of this element. Such differences have important implications in assessing the current and future role of atmospheric inputs in affecting elemental cycling.     

Seasonal Evolution of Levels of Gaseous Pollutants in an Urban Area (Ciudad Real) in Central-Southern Spain: A Doas Study

Long term continuous monitoring measurements of urban atmospheric concentrations of O₃, NO₂, NO, and SO₂ were performed for the first time in Ciudad Real, a city in central-southern Spain. The measurements were carried out using the differential optical absorption spectroscopy (DOAS) technique, with a commercial system (OPSIS, Lund-Sweden), covering the summer and winter seasons (from 21st July 2000 to 23rd March 2001). Mean levels of O₃, NO₂ and SO₂ monitored during this period were: 27 μg m^?3, 50 μg m^?3 and 7 μg m^?3 respectively. The highest hourly averaged value of O₃ (160 μg m^?3) was measured during the summer period, while NO₂ was enhanced in wintertime (highest values 90 μg m^?3). In the coldest period, when central heating installations were operating, SO₂ showed maximum levels of 20 μg m^?3. The daily, weekly and seasonal analysis of the data shows that photochemical air pollution dominates in this urban atmosphere and is strongly influenced by levels of motor traffic and domestic heating system emissions. These measurements were compared with other studies in Spain and Europe. Also, the long path averaged DOAS measurements were compared with in situ observations made in Ciudad Real, from 23rd August 2000 to 25th September 2000, using a mobile air pollution control station. All gas concentrations reported in this paper are below the WHO guidelines and the different thresholds introduced by the European Environmental Legislation.