Biogeochemistry of two Appalachian deciduous forest sites in relation to episodic stream acidification

Bulk precipitation, throughfall, and soil water chemistry were studied from November 1983 to November 1984 at two ridge-top Appalachian deciduous forest sites to isolate causes of differing episodic stream acidification. The Fork Mountain site in West Virginia, which exhibited little episodic stream acidification, had lower deposition of H⁺ and SO _inf4 ^sup2? and greater reductions of H⁺ in the water circulating through the forest canopy, forest floor, and mineral soil than the Peavine Hill site in Pennsylvania. Greater neutralization at Fork Mountain was linked to higher Ca and Mg carbonate contents in the sandstone and shale soil parent materials. Fork Mountain had greater amounts of exchangeable bases in the organic and mineral soil horizons. Neither site appeared to be accumulating SO _inf4 ^sup2? in the soil, with Peavine Hill losing 56% more than was received in bulk deposition. Anions in soil leachate at Fork Mountain were largely balanced by Ca²⁺ and Mg²⁺, while at the Peavine Hill site A1" was the dominant cation. Results suggest that the typically-low carbonate content of sandstone and shale soil parent materials commonly found in Appalachian forests may be a key parameter controlling soil and stream acidification. Data for the one-year period also suggest bulk deposition of H⁺ was 63% greater at Peavine Hill than Fork Mountain.     

Canopy leaching of cations in Central European forest ecosystems – a regional assessment

The leaching of Ca, Mg, and K from canopies is a major pathway of these cations into forest soils. Our aim was to quantify rates of canopy leaching and to identify driving factors at the regional scale using annual fluxes of bulk precipitation and throughfall from 37 coniferous and deciduous forests of North and Central Europe. Total deposition of Ca, Mg, K, and H⁺ was estimated with Na as an index cation. The median canopy leaching increased in the order: Mg (0.11 kmol_c ha^–1 a^–1) < Ca (0.31 kmol_c ha^–1 a^–1) < K (0.39 kmol_c ha^–1 a^–1). Canopy leaching of Ca and K was positively correlated with the calculated total H⁺ deposition and H⁺ buffered in the canopy, whereas canopy leaching of Mg was not. With contrasting effects, fluxes of SO₄‐S and NH₄‐N in throughfall explained to 64 % (P<0.001) of the Ca canopy leaching. Fluxes of NH₄‐N and Ca were negatively correlated, suggesting that buffering of H⁺ by NH₃ deposition reduced canopy leaching of Ca. Amount of bulk precipitation and SO₄‐S in throughfall were identified as much weaker driving factors for canopy leaching of K (r²=0.28, P<0.01). Our results show that Ca is the dominant cation in buffering the H⁺ input in the canopy. At the regional and annual scale, canopy leaching of Mg appears to be unaffected by H⁺ deposition and H⁺ buffering in the canopy.     

The role of organic horizons and canopy to modify the chemistry of acidic deposition in some forest ecosystems

To clarify the mechanisms of pH buffering in forest ecosystems, field observations of pH and ionic concentrations in precipitation (R), throughfall (Tf), stemflow (Sf), and leachates from organ c horizons (Lo) were conducted for three years at three stands in Tomakomai (TK) and Teshio (TS) in Hokkaido, northern Japan. Weighted mean rates of H⁺ input as wet deposition at TK and TS were estimated in the range from 0.3 to 1.0 and 0.4–0.6 kmol_c ha^?1 y^?, respectively. While the net H⁺ flux was reduced significantly by the forest canopy, net fluxes of other ions by throughfall, especially for Na⁺, Cl^?, and SO₄ ^2?, were apparently greater than those by precipitation. The canopy modification of the H⁺ flux was more remarkable under deciduous stands than under coniferous stands, suggesting that the efficiency of conifers as the collectors of dry deposition is greater than that of deciduous ones. More than 50% of H⁺ flux due to throughfall was absorbed by the organic horizons and the weighted mean pH of Lo at TK and TS was in the range from 4.9 to 5.5 and 5.0–5.5, respectively. Results from field observation and field leaching experiments, showed that the major H⁺ sinks of the organic horizons are exchange reaction of Ca²⁺, Mg²⁺ and K⁺. Organic acids or organo-metallic complexes of lower pK(=5.0–5.5) played a significant role as counter anions in O horizons leachate in coniferous forests. Our results indicate the importance of biogeochemical modifications in the canopy and organic horizon in acid buffering mechanisms of forest ecosystems.     

The geographical distribution and temporal variations of acidic deposition in Eastern North America

Data from two national precipitation chemistry monitoring networks, and several regional air and precipitation chemistry networks are used to describe some broad-scale features of acidic deposition in eastern North America. In northeastern North America, the coefficient of variation is shown to increase from 10–16% for annual averages to nearly 100% for daily values. There is a strong annual cycle in H⁺, SO _inf4 ^sup= and NH _inf4 ^sup+ deposition and some of the other ions although these cycles are not all in phase. The wet NO _inf3 ^sup? deposition contributes relatively more than SO _inf4 ^sup= to the acidity of snow as compared to rain. Wet deposition is highly “episodic” with about 50% to 70% of the total annual deposition of SO _inf4 ^sup= and NO _inf3 ^sup? accumulating in the highest 20% of the days. Estimates made in various ways indicate that, over eastern North America as a whole, dry deposition is approximately equal to wet for both SO _inf4 ^sup= and NO _inf3 ^sup? . Dry may exceed wet in the high emissions zone but drops to about 20% of the total deposition in more remote areas. Deposition via fog or low cloud impaction is an important input to high elevation forests, but more data are required to quantify the magnitude and regional extent of this.     

Ion mass budgets for small forested catchments in Finland

Ion mass and H⁺ budgets were calculated for three pristine forested catchments using bulk deposition, throughfall and runoff data. The catchments have different soil and forest type characteristics. A forest canopy filtering factor for each catchment was estimated for base cations, H⁺, Cl^? and SO ₄ ^2? by taking into account the specific filtering abilities of different stands based on the throughfall quality and the distribution of forest types. Output fluxes from the catchments were calculated from the quality and quantity of the runoff water. Deposition, weathering, ion exchange, retention and biological accumulation processes were taken into account to calculate catchment H⁺ budgets, and the ratio between external (anthropogenic) and internal H⁺ sources. In general, output exceeded input for Na⁺, K⁺, Ca²⁺, Mg²⁺, HCO ₃ ^? (if present) and A^? (organic anions), whereas retention was observed in the case of H⁺, NH ₄ ⁺ , NO ₃ ^? and SO ₄ ^2? . The range in the annual input of H⁺ was 22.8–26.3 meq m^?2 yr^?1, and in the annual output, 0.3–3.9 meq m^?2 yr^?1. Compared with some forested sites located in high acid deposition areas in southern Scandinavia, Scotland and Canada, the catchments receive rather moderate loads of acidic deposition. The consumption of H⁺ was dominated by base cation exchange plus weathering reactions (41–79 %), and by the retention of SO ₄ ^2? (17–49 %). The maximum net retention of SO ₄ ^2? was 87% in the HietajÄrvi 2 catchment, having the highest proportion of peatlands. Nitrogen transformations played a rather minor role in the H⁺ budgets. The ratio between external and internal H⁺ sources (excluding net base cation uptake by forests) varied between 0.74 and 2.62, depending on catchment characteristics and acidic deposition loads. The impact of the acidic deposition was most evident for the southern Valkeakotinen catchment, where the anthropogenic acidification has been documented also by palaeolimnological methods.     

Precipitation chemistry in Nova Scotia: 1978–1987

More than 1400 precipitation samples were collected weekly from 5 sites in Nova Scotia between 1978 and 1987. High concentrations of H⁺, non-marine SO _inf4 ^sup= (^*SO₄) and NO _inf3 ^sup- were observed in 1978 and 1986. In 1983, concentrations of all three parameters were the lowest in the data record. Fluctuations in emissions for SO₂ are insufficient to account for the variability observed in concentration and deposition values. Mean annual concentrations in 1983 were 13, 16, and 6 ueq L^-1 for H⁺, ^*SO₄, and NO _inf3 ^sup- , respectively. In 1986 the values were 35, 28, and 13 ueq L^-1. Concentrations in 1978 were 31, 38, and 16 ueq L^-1. Average pH of precipitation was 4.61 during the 10 yr study. The two most acidic years were 1979 (4.47) and 1986 (4.46). In 1983, the average pH was 4.89. The ratio (equivalents) of NO _inf3 ^sup- to ^*SO4 was 0.41, so most acidity in the precipitation results from H₂SO₄ However, multiple regression analysis revealed that H⁺ is more sensitive to changes in NO₃-concentrations than ^*SO₄. Ratios of summer (JJA) vs winter (JFM) average concentrations were examined. During summer months, ^*SO₄ and H⁺ were 1.8 times winter values. Summer to winter ratios for NO _inf3 ^sup- and NH _inf4 ^sup+ were 1.4 and 2.5, respectively.     

A method for evaluation of acidic sulfate and nitrate in precipitation

A simple method is presented and used to estimate the portions of SO _inf4 ^sup2? and NO _inf? ^sup3 that contribute to the strong acidity in weekly precipitation samples collected at three NADP sites in the eastern United States. The method assumes that, in general, the difference between SO _inf4 ^sup2? and NH _inf+ ^sup4 represents acidic sulfate and the difference between NO _inf? ^sup3 and soil-derived materials (the sum of Ca²⁺, Mg²⁺, and K⁺) represents acidic nitrate. Acidic sulfate and nitrate are considered to be the predominant source of H⁺ (determined from laboratory pH) in the weekly precipitation samples. Most of the acidity for all three sites was attributed to acidic sulfate. The highest fraction of acidic SO _inf4 ^sup2? to H⁺ wet deposition values was for the east-central Tennessee site (0.95) and the northeastern Illinois site (0.90), and the lowest fraction occurred at the central Pennsylvania site (0.75). The Tennessee site had the greatest acidic fraction of sulfate (0.84) and the Pennsylvania site had the greatest acidic fraction of nitrate (0.59).     

Element Inputs and Canopy Interactions in two Pine Forest Ecosystems in Berlin,Germany

For 3 years (1986-89), element fluxes with bulk deposition and throughfall were determined in a 40 yr. old pine plantation and a 80-140 yr. old mixed pine/oak stand in the Grunewald forest in Berlin. Although SO₄-inputs are very high (60 kg S·ha^?1.a^?1) due to the urban character of the study site, acid inputs are moderate because of the buffering action of airborne alkaline dusts. This is reflected in the high Ca-inputs (12 kg·ha^?1a^?1 in bulk precipitation). Acid neutralisation was also observed in the canopies and could be attributed to 60-80% to increased Ca- and Mg-fluxes in throughfall, stemming from foliage leaching and dust interception. Heavy metal inputs were low in comparison to other Central European study sites, the decrease in Pb-inputs over the 3-year period could be attributed to the increased use of unleaded gasoline since 1987. Total inputs and canopy leaching showed clear seasonal patterns for some elements: SO₄-, H-, Ca- and Mg-fluxes were higher in winter, on the other hand, K- and Mn-enrichment in throughfall showed two peaks, in early summer and late fall.     

Atmospheric Deposition of Acidifying Components to a Japanese Cedar Forest

One-year field measurements were conducted in a Japanese cedar (Cryptomeria japonica) forest, located in Gunma Prefecture, Japan. On the basis of the meteorological and atmospheric concentration data, the dry deposition of SO₂, HNO₃, NO₂ and HCl was estimated using the inferential method. The annual dry deposition of H⁺ was estimated at 721 eq ha^?1yr^?1, which was 40% larger than the measured annual wet deposition of H⁺ (514 eq ha^?1yr^?1). Therefore, dry deposition is an important pathway for the atmospheric input of H⁺ to the forest in the study site. The contribution of each gas to the dry deposition of H⁺ was as follows: SO₂, 25%; HNO₃, 32%; NO₂, 10%; and HCl, 33%. The extremely high contribution of HCl appeared to be caused by the high emission intensity of HCl due to waste incineration in the site region. The differences between estimated deposition and throughfall and stemflow measurements indicated that about 80% of the total deposition of H⁺ was taken up by the canopy.     

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.     

Elevational trends in the fluxes of sulphur and nitrogen in throughfall in the Southern Appalachian Mountains: Some surprising results

From 1986–1989, a team of scientists measured atmospheric concentrations and fluxes in precipitation and throughfall, and modeled dry and cloudwater deposition in a spruce-fir forest of the Great Smoky Mountains National Park which is located in the Southern Appalachian Region of the United States. The work was part of the Integrated Forest Study (IFS) conducted at 12 forests in N. America and Europe. The spruce-fir forest at 1740 m consistently received the highest total deposition rates (～2200, 1200, and 700 eq ha^?1 yr^?1 for SO₄ ^2?, NO₃ ^?, and NH₄ ⁺). During the summers of 1989 and 1990 we used multiple samplers to measure hydrologie, SO₄ ^2?, and NO₃ ^? fluxes in rain and throughfall events beneath spruce forests above (1940 m) and below (1720 m) cloud base. Throughfall was used to estimate total deposition using relationships determined during the IFS. Although the SO₄ ^2? fluxes increased with elevation by a factor of ～2 due to higher cloudwater interception at 1940 m, the NO₃ ^? fluxes decreased with elevation by ～30%. To investigate further, we began year round measurements of fluxes of all major ions in throughfall below spruce-fir forests at 1740 m and at 1920 m in 1993–1994. The fluxes of most ions showed a 10–50% increase with elevation due to the ～70 cm yr^?1 cloudwater input at 1920 m. However, total inorganic nitrogen exhibited a 40% lower flux in throughfall at 1920 m than at 1740 m suggesting either higher dry deposition to trees at 1740 m or much higher canopy uptake of nitrogen by trees at 1920 m. Differential canopy absorption of N by trees at different elevations would have significant consequences for the use of throughfall N fluxes to estimate deposition. We used artificial trees to understand the foliar interactions of N.     

Nutrient Fluxes in Planted Norway Spruce Stands of Different Age in Southern Poland

The fluxes of N–NO ₃ ^? , N–NH ₄ ⁺ , S–SO ₄ ^2? , Na⁺, K⁺, Ca²⁺ and Mg²⁺ from bulk precipitation to throughfall, stemflow and soil water surface flows were studied during 1999–2003 in planted Norway spruce forest stands of different ages (11, 24, 91 and 116 years in 1999). Also, runoff from the corresponding Potok Dupniański Catchment in the Silesian Beskid Mts was studied. N deposition was above the critical load for coniferous trees. The interception increased with stand age as well as leaf area index and so did the leaching from the canopy of almost all the analysed elements, but especially S–SO ₄ ^2? , H⁺ and K⁺. The nutrient fluxes varied with age of the spruce stands. Throughfall showed a high amount of S and of the strong acids (S–SO ₄ ^2? and N–NO ₃ ^? ) deposited to the soil, especially in older spruce age classes. Decomposition of organic matter caused a rise in water acidity and an increase in the concentrations of all the analysed ions; the leaching of minerals, however, was low (under 1%). The horizontal soil water flow showed an increase in the amount of water and amount of ions and contributed to a further decrease of pH at the soil depth of 20 cm. Element concentrations and their amounts increased with water penetrating vertically and horizontally on the slopes. Considerable amounts of ions, especially S and alkaline cations, were carried beyond the reach of the root system and then left the catchment. In the long term, these mineral losses will adversely affect health and growth of the spruce stands, and the increased acidity with stand age will presumably have negative effects on the runoff water ecosystem.     

Vegetation,soils, and ion transfer through the forest canopy in two Nova Scotia lake basins

Characterization of the forest vegetation and soils in two adjacent; contrasting headwater lake basins located in Kejimkujik National Park, Nova Scotia was completed in 1980. Precipitation chemistry was studied during May to November, 1981–83 at two forested plots in each basin. There were 2012 stems ha^-1 in Beaverskin basin and 1816 stems ha^-1 in Pebbleloggitch basin. Beaverskin species composition was predominantly coniferous (72% of stems) while Pebbleloggitch was predominantly deciduous (52% of stems). Thickness and mass of organic soil layers were greater in Beaverskin. Mineral soil cation concentrations were similar. There were no differences between the basins in mean incident bulk precipitation pH. Mean volume-weighted pH for the period (73 collections) was 4.80. Sixteen percent of collections had a pH < 4.25. Sulphate deposition in incident bulk precipitation (May – November) ranged from 5.4–8.5 kg ha^-1 during 1981–83 while NO _inf3 ^sup- ranged from 0.04–0.93 kg ha^-1. The partitioning of incident precipitation into throughfall varied considerably (69%–38%) year-to-year. Temporal flux of ions did not differ significantly. Amounts of all major ions in throughfall especially SO _inf4 ^sup2- and base cations(Ca²⁺ + Mg²⁺ + K⁺ + Na⁺) were enriched.     

Deposition of air pollutants in a wind-exposed forest edge

The atmospheric deposition of air pollutants at a forest edge was studied by means of monitoring canopy throughfall at the edge and at five different parallel lines in the forest behind the edge. The investigation was carried out at a pine forest on the Swedish west coast. Throughfall and bulk deposition samples were analyzed for volume, SO ₄ ^2? , NO ₃ ^? , Cl^?, NH ₄ ⁺ , Na⁺, K⁺, Mg²⁺, Ca²⁺, and for pH. The results show that the throughfall flow at the edge was increased substantially for most ions. The ratios in throughfall flows between the edge and the line 50 m into the forest were for SO ₄ ^2? , 1.5, NO ₃ ^? 2.9, NH ₄ ⁺ 2.7, and Na⁺ 3.1. Since this effect is not only valid for forest edges but also for hillsides, hilltops, and edges between stands of different age, etc., there might be substantial areas which get much larger total deposition than the normally considered closed forest.     

Sources of acidity in forest-floor percolate from a maple-birch ecosystem

Ion concentrations in water collected within a forest of sugar maple and yellow birch at the Turkey Lakes Watershed near Sault Ste. Marie, Ontario were examined from 1982 to 1984 to determine sources of acidity and the extent of cation leaching from forest floor horizons. Volume-weighted concentrations and ion fluxes in throughfall and forest-floor percolate during the growing and dormant seasons were calculated. Hydrogen ion content of the forest-floor percolate decreased in relation to that of throughfall in the dormant season and increased in the growing season. Hydrogen ion deposition in throughfall could account for 100% of the flux of H⁺ through the forest floor in the dormant period, and 40% of the flux during the growing season. In forest-floor percolate, Ca²⁺ concentrations were positively correlated with those of SO₄ ^2-, NO₃ ^- and organic anions during both dormant and growing seasons. Sources of NO₃ ^- and organic anions within the ecosystem and major external inputs of NO₃ ^- and SO₄ ^2- were critical factors that influenced cation mobility in the forest floor.     

Estimates of atmospheric deposition and canopy exchange for three common tree species in the Netherlands

During one year, dry and wet deposition onto thirty forest stands is studied by sampling throughfall and bulk precipitation. Nine measurement sites are situated in Douglas fir (Pseudotsuga menziesii Mirb. Franco) stands, ten in Scotch pine (Pinus sylvestris L.) and eleven in Oak (Quercus robur L.) stands. Because the stands are situated in each other's proximity (i.e. within a radius of approximately 1.4 km) it is assumed that they experience an approximately equal air pollution load. For the acidifying compounds SO₄ ^2?, NO₃ ^? and NH₄ ⁺ spatial variability in wet deposition was small within the area studied. Dry deposition, as estimated by net throughfall, displayed a much higher spatial variability. Significant differences existed between tree species and growing seasons. Douglas fir mostly displayed the highest, Oak the lowest and Scotch pine intermediate values for net throughfall fluxes of acidifying compounds. The annual net throughfall fluxes for nitrogen compounds were significantly higher for the coniferous tree species than the broadleaved tree species. For SO₄ ^2?, however, Oak showed a relatively high throughfall flux during the summer. By comparing the temporal pattern of net throughfall fluxes between the three tree species it was concluded that considerable canopy leaching occurred for SO₄ ^2?, Mg⁺, PO₄ ^3?, HCO₃ ^? and K⁺ in Oak stands during the sprouting of leaves in spring. From surface wash experiments in the laboratory it is concluded that canopy leaching of these ions may also be enhanced when Oak leaves are infected by Oak mildew, a fungal disease caused by the fungus Microshaera aliphilitoides.     

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.     

Effects of Weak Acids on Canopy Leaching and Uptake Processes in a Coniferous-Deciduous Mixed Evergreen Forest in Central-South China

The effects of Weak acids (WA) on the canopy leaching and uptake processes are evaluated by comparing the leached base cations or the absorbed protons while including and excluding WA, e.g. the WA-included method and the WA-excluded method. The seasonal WA throughfall flux is even larger than twice the bulk precipitation flux except summer, which not only partly agrees with the conclusion that the total deposition of WA equals twice the bulk or dry deposition flux in European Intensive Monitoring plots (level II), but also indicates the significant canopy leaching of WA in Shaoshan forest. The seasonal canopy leaching of base cations in association with WA accounts for 6–30% of the total base cations in throughfall, with an annual mean of 23%, which is slightly higher than the 15% at the Speulder forest in The Netherlands. The canopy exchange capacity of H⁺ to NH₄ ⁺ is closed to 6.0 while neglecting the WA exchange, which probably supports the assumption that the exchange capacity of H⁺ is six times that of NH₄ ⁺. Simultaneously, we suggest that the WA is competitive to a certain extent with protons to leach base cations of plant tissues during the canopy exchange processes.     

An estimation of atmospheric deposition input of sulphur and nitrogen oxides to the Kejimkujik watershed : 1979–1987

Daily measurements of the concentrations of major ions in ambient air and in precipitation at Kejimkujik National Park, Nova Scotia, Canada over the period May 1979 to December 1987 are used to estimate the wet, dry and total deposition to the watershed. Variations on three time-scales are apparent. The strongest variation, of up to two orders of magnitude occurs on a day to day basis resulting in a coefficient of variation in the range of 110 to 140%. Deposition is highly episodic with the highest 20% of the daily events accounting for 55 to 60% of the long-term deposition. The most systematic variation is the annual cycle observed for many of the species. The air concentration of SO₂ has the most pronounced cycle with a winter maximum and a summer minimum. The SO _inf4 ^sup= air concentrations show a smaller amplitude and are out-of-phase with SO₂, showing a summer maximum. Air concentrations of HNO₃ and particulate N0 _inf3 ^sup- also have an out-of-phase annual cycle, with a summer maximum and summer minimum respectively. Wet deposition of SO _inf4 ^sup= shows a broad maximum through the summer months, but for NO _inf3 ^sup- no systematic cycle is evident. On an ion equivalent basis, NO _inf3 ^sup- contributes as much as SO _inf4 ^sup= to the acidity of winter precipitation, but only one-third as much in the summer months. Although 8.7 yr is too short a time-scale to establish long term variations with any certainty, there does appear to be an overall downward trend in S concentrations and deposition, but not for N. This is not inconsistent with the trends in the emissions of SO₂ and NO_X in the regions upwind of Nova Scotia. The fraction of the S input to the watershed as dry deposition is estimated to average 22% of the total.     

Water,nutrient and pollutant budgets in damaged Norway spruce stands in NE-Bavaria (F.R.G.) and their changes after different fertilization treatments

Water budgets and ecosystem balances of the main nutrients and pollutants were calculated in two Norway spruce forests at different states of decline in the Fichtelgebirge (F.R.G.) from summer 1984 through summer 1986. For that purpose, samples of precipitation, throughfall, litter seepage and soil solution were gathered weekly. Fluxes of main cations and anions were calculated by multiplying water fluxes through the different compartments with the appropriate ion concentrations. Both spruce stands are characterized by a sufficient water supply throughout the investigation period caused by high annual precipitation. Only in dry periods drastical restriction of plant available water may endanger those spruces growing on very stony podzols and cambisols. The calculation of deposition fluxes differentiates the damaged and the apparently healthy spruce stand. Input of SO₂ and H⁺ as well as canopy buffering and K-leaching of the canopies are significantly higher in the damaged spruce stand than in the healthy one. Additionally, the exchangeable base cation content of the soil on the damaged site is nearly exhausted and therefore buffering capacity in the soil differs from those of the healthy site. There was a low increase of N0₃-leaching with seepage after the fertilization with high amounts of lime.