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.     

Examination of the Dissolved Inorganic Nitrogen Budget in Three Experimental Microbasins with Contrasting Land Cover—A Mass Balance Approach

A long-term hydrological and water chemistry research was conducted in three experimental microbasins differing in land cover: (1) a purely agricultural fertilized microbasin, (2) a forested microbasin dominated by Carpinus betulus (European hornbeam), and (3) a forested microbasin dominated by Picea abies (L.) (Norway spruce). The dissolved inorganic nitrogen (DIN: NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? ) budget was examined for a period of 3 years (1991–1993). Mean annual loads of DIN along with sulfate SO ₄ ^2? and base cations Ca²⁺, Mg²⁺, Na⁺, K⁺, and HCO ₃ ^? were calculated from ion concentrations measured in stream water, open-area rainfall, throughfall (under tree canopy), and streamwater at the outlets from the microbasins. Comparison of the net imported/exported loads showed that the amount of NO ₃ ^? leached from the agricultural microbasin is ～3.7 times higher (43.57 kg ha^?1?a^?1) than that from the spruce dominated microbasin (11.86 kg ha^?1?a^?1), which is a markedly higher export of NO ₃ ^? compared to the hornbeam dominated site. Our analyses showed that land cover (tree species) and land use practices (fertilization in agriculture) may actively affect the retention and export of nutrients from the microbasins, and have a pronounce impact on the quality of streamwater. Sulfate export exceeded atmospheric rainfall inputs (measured as wet deposition) in all three microbasins, suggesting an additional dry depositions of SO ₄ ^2? and geologic weathering.     

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.     

Nitrogen Leaching of Two Forest Ecosystems in a Karst Watershed

Karst watersheds are a major source of drinking water in the European Alps. These watersheds exhibit quick response times and low residence times, which might make karst aquifers more vulnerable to elevated nitrogen (N) deposition than non-karst watersheds. We summarize 13 years of monitoring NO ₃ ^? , NH ₄ ⁺ , and total N in two forest ecosystems, a Norway spruce (Picea abies (L.) Karst.) forest on Cambisols/Stagnosols (IP I) and a mixed beech (Fagus sylvatica L.) spruce forest on Leptosols (IP II). N fluxes are calculated by multiplying concentrations, measured in biweekly intervals, with hydrological fluxes predicted from a hydrological model. The total N deposition in the throughfall amounts to 26.8 and 21.1 kg/ha/year in IP I and IP II, respectively, which is high compared to depositions found in other European forest ecosystems. While the shallow Leptosols at IP II accumulated on average 9.2 kg/ha/year of N between 1999 and 2006, the N budgets of the Cambisols/Stagnosols at IP I were equaled over the study period but show high inter-annual variation. Between 1999 and 2006, on average, 9 kg/ha/year of DON and 20 kg/ha/year of DIN were output with seepage water of IP I but only 4.5 kg/ha/year of DON and 7.7 kg/ha/year of DIN at IP II. Despite high DIN leaching, neither IP I nor IP II showed further signs of N saturation in their organic layer C/N ratios, N mineralization, or leaf N content. The N budget over all years was dominated by a few extreme output events. Nitrate leaching rates at both forest ecosystems correlated the most with years of above average snow accumulation (but only for IP I this correlation is statistically significant). Both snow melt and total annual precipitation were most important drivers of DON leaching. IP I and IP II showed comparable temporal patterns of both concentrations and flux rates but exhibited differences in magnitudes: DON, NO ₃ ^? , and NH ₄ ⁺ inputs peak in spring, NH ₄ ⁺ showed an additional peak in autumn; the bulk of the annual NO ₃ ^? and DON output occurred in spring; DON, NO ₃ ^? , and NH ₄ ⁺ output rates during winter months were low. The high DIN leaching at IP I was related to snow cover effects on N mineralization and soil hydrology. From the year 2004 onwards, disproportional NO ₃ ^? leaching occurred at both plots. This was possibly caused by the exceptionally dry year 2003 and a small-scale bark beetle infestation (at IP I), in addition to snow cover effects. This study shows that both forest ecosystems at Zöbelboden are still N limited. N leaching pulses, particularly during spring, dictate not only annual but also the long-term N budgets. The overall magnitude of N leaching to the karst aquifer differs substantially between forest and soil types, which are found in close proximity in the karstified areas of the Northern Limestone Alps in Austria.     

Analysis of Decadal Time Series in Wet N Concentrations at Five Rural Sites in NE Spain

Nitrogen emissions have grown in Spain during the last 15 years. As precipitation scavenges gases and aerosols from the atmosphere, an effect on rainwater concentrations can be expected. However, time-series studies on wet N concentrations in the Iberian Peninsula are very scarce. This paper aims to fill this gap by analysing weekly rainfall N concentrations at a set of rural sites in Catalonia (NE Spain) from 1995/1996 to 2007 and a forest site monitored from 1983 to 2007. The sites encompass a range of rural environments and climate conditions, from the inland pre-Pyrenees (Sort) to the Mediterranean coast (Begur) and from north (Sort and Begur) to central (Palautordera and La Castanya) and south Catalonia (La Senia). We found a 1-year cycle for concentrations of NH ₄ ⁺ and NO ₃ ^? whereby higher values were reached at the end of spring–early summer, except at the easternmost coastal site of Begur. Weekly NH ₄ ⁺ concentrations decreased with time at all sites (except at La Senia) whilst NO ₃ ^? concentrations increased at all sites during the same period. Rainfall SO ₄ ^2? concentrations decreased with time at all sites. The opposite trends in NO ₃ ^? and SO ₄ ^2? concentrations determined a shift in the relative acid contribution of those anions during the 12–13-year period. To interpret the increasing trend, mean annual NO ₃ ^? concentrations were regressed against NO₂ Spanish emissions and to some indicators of local anthropogenic activity. The increase at Sort and Palautordera showed good correlation with local anthropogenic indicators. Wet inorganic N deposition ranged between 4.2 and 6.7 kg ha^?1 year^?1. When including estimates of dry deposition, total annual deposition rose up to 10–20 kg ha^?1 year^?1, values that have been found to initiate adverse effects on Mediterranean-type forest ecosystems.     

Forest canopy transformation of atmospheric deposition

Solute fluxes to the ground in open plots and under the forest canopy of different species were investigated in a number of long-term ecosystem studies in West Germany. From the canopy flux balance, rates of interception deposition and canopy/deposition interactions were assessed. Chemically, both open precipitation and throughfall are dilute solutions of H₂SO₄ and HNO₃ and their salts. For the sites investigated, mean pH in bulk precipitation ranged from 4.1 to 4.6, and in throughfall from 3.4 to 4.7. The increase in acidity after canopy passage at most sites indicates considerable interception deposition of strong acids to the forest stands, exceeding the rate of H+ buffering in the canopy. Evidence for buffering processes can be directly deduced from the fact that on sites with high soil alkalinity and high foliage base status, throughfall pH is usually higher than precipitation pH. Furthermore, the same idea can be concluded from changes in solution composition after canopy passage: the H⁺/SO _inf4 ^sup2? ratio is decreasing at most sites, while alkali earth cations from exchange processes occur in throughfall (Ca²⁺/SO _inf4 ^sup2? ratio increases). Solution composition and element flux data are presented for each of the sites, and the regional, orographical and site specific (species composition, ecosystem state) differentiations are discussed. A method for the assessment of total deposition and of canopy interactions such as H⁺-buffering and cation leaching is described, and results of calculations are shown. From these calculations it is concluded that forest ecosystems in Germany receive mean H⁺ loads of ca. 1 to 4 keq H⁺ · ha^?1 · a^?1 from atmospheric deposition. Acidity deposition rates seem to be related to a few key factors such as regional characteristics and ecosystem characteristics.     

Stream chemistry impacts of conifer harvesting in welsh catchments

Hydrochemical data have been collected for between 6 and 9 years from forest harvesting experiments in small catchments (>10 ha) at Plynlimon and Beddgelert, Wales, UK. Felling resulted in rapid increases in NO ₃ ^? and K⁺ concentrations at both sites. A maximum of 3.2 mg N L^?1 was observed at Plynlimon about one year after the start of felling. Concentrations declined to control stream values (0.5 mg N L^?1) after 5 years. At Beddgelert, NO ₃ ^? concentrations in the manipulated catchments remained above those in the unfelled control catchment for three years, before declining below control values. The NO ₃ ^? pulse was related to increased rates of mineralization and nitrification in the soil after felling. The initial increase in K⁺ concentration after felling at Plynlimon was followed by a slow decline, but concentrations were still above those in the control stream after 5 years. From 4 to 8 years after felling at Beddgelert, K⁺ concentrations fell below and then generally remained lower than control values. The NO ₃ ^? pulse after felling at Plynlimon sustained inorganic anion concentrations above those in the control stream for the first 18 months after felling. As the NO ₃ ^? pulse declined, inorganic anion concentrations decreased to below those in the control stream about 4 years after felling. At Beddgelert, the smaller increase in NO ₃ ^? concentrations had less of an effect on inorganic anion concentrations which decreased after felling relative to values in the control stream. The increase in NO ₃ ^? was associated with temporary streamwater acidification in the felled catchments due to the increased rates of nitrification and nitrate leaching. At Plynlimon, streamwater filterable Al concentrations declined after felling, but controls on Al behaviour are complex and not explained by simple equilibrium relationships with Al(OH)₃ or by variations in inorganic anion concentrations. At Beddgelert, felling had no effect on stream water filterable Al concentrations. Felling at Plynlimon led to a large reduction in streamwater Cl^?, Na⁺ and SO ₄ ^2? concentrations. At Beddgelert reductions in SO ₄ ^2? and ‘sea salt’ ion concentrations were less clear, reflecting the smaller proportions of the catchments which were harvested. Felling had no deleterious effects on water quality, apart from a temporary slight further decline in stream pH at Beddgelert. Increases in NO ₃ ^? concentrations were short-lived and concentrations were well below drinking water standards. Filterable Al concentrations were already higher than statutory standards, but were not increased or decreased through felling.     

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.     

Chemical composition of precipitation in a forest area of Chongqing,Southwest China

Experiments were carried.out in Chongging-a city seriously damaged by acid precipitation in southwest China — to explore chemical compositions of open bulk precipitation, throughfall and stemflow in a Masson pine (Pinus massoniana) forest. The results showed that annual mean pH values of and annual ion depositions in the three types of rain water were 4.47 and 50.6 g m^?2, 3.82 and 69.7 g m^?2, and 2.92 and 0.215 g m^?2 respectively. pH values demonstrated an obvious seasonal variation; they were lower in winter than in the rest of the year. Ca²⁺ and NH _inf4 ^sup+ together made up more than 80% of the total cation, while SO _in4 ^sup2? alone contributed over 90% to the total anion. This high level of SO _in4 ^sup2? in rain water in Chongqing, which outran those found in other cities in China, was closely related to the combustion of locally produced coal that contains 3 to 5% sulphur. Thus, acid precipitation in Chongqing is of a typical sulphuric-acid type.     

Recent Atmospheric Deposition and its Effects on Sandstone Cliffs in Bohemian Switzerland National Park, Czech Republic

The protected area ??Bohemian Switzerland National Park?? with its characteristic sandstone landscape was influenced by the long-term air pollution and acidic deposition within the area known as Black Triangle (located where Germany, Poland, and the Czech Republic meet, is one of the Europe??s most polluted areas). The local Upper Cretaceous sandstone is subhorizontally stratified, fine- to coarse-grained, quartz dominated, with low content of clay minerals. One of the significant negative effects of the intensive acidic deposition on sandstone outcrops has been identified as chemical (salt) weathering, i.e., a process when the porous sandstone rock is except of chemical influence attacked also by force of crystallization of growing salts crystals. Anions NO ₃ ^? together with SO ₄ ^2? and cation NH ₄ ⁺ were the most abundant solutes in bulk precipitation samples. Current (2002 to 2009) bulk deposition fluxes of SO ₄ ^2? determined at three sites directly in the National Park indicate decline from 23 to 16 kg^?1 ha^?1 year^?1. Infiltration of bulk precipitation solutes into the sandstone mediates the weathering processes. Natural outflow of sandstone pore-water (sandstone percolates) can be sampled only during certain days of year when the sandstone becomes saturated with water and percolates drip out on small number of sites from roofs of overhangs. Under usual conditions percolation water evaporates at the sandstone surface producing salt efflorescences??the typical example is Prav?ická brána Arch locality. The average pH of the dripping sandstone percolates was 3.76. Concentration of SO ₄ ^2? and Al in sandstone percolates reached up to 46 and 10 mg L^?1. The concentration of Al in percolates has been 160-fold greater the one in the precipitation samples suggesting the sandstone as a source. The water O and H isotopic composition of percolates has been virtually identical to precipitation samples, indicating thus relatively short residence time of the solutions within the sandstone pore-spaces. Evaporation experiments with bulk precipitation and percolate samples proved possible origin of some Ca in bulk precipitation and the sandstone rock as the source of Al and possibly of K for the salt efflorescence identified on Rock Arch body.     

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.     

A preliminary assessment of nitrogen-based fresh water acidification in southeastern Canada

Sulphate deposition is the primary cause of acidification in northeastern North America, and new SO₂ emission control is being implemented. However, continuation of existing levels of N deposition may undermine the environmental benefits derived from SO₂ control. This likelihood has been assessed for Canadian lakes. Maximum N deposition (～13 kg N ha^?1 yr^?1) occurs in south-central Ontario and southwestern Quebec. Regional median NO ₃ ^? levels are generally low (<5 μeq L^?1) suggesting that on average, N-based acidification is minor compared to the S-based component. However, examination of the seasonal NO ₃ ^? pattern at 5 intensively monitored basins reveals that 2 of them (in Ontario and Quebec) have incipient N saturation. A regional status for nitrogen-based acidification was qualitatively assessed by classifying survey data to identify cases of NO ₃ ^? leaching. Many lakes throughout southeastern Canada exhibit some leaching, particularly those in south-central Ontario and southwestern Quebec. While the evidence for a deposition-acidification link appears strong, sources of N other than the atmosphere should be considered for certain anomalous cases.     

Effects of simulated throughfall pH and sulfate concentration on a deciduous forest soil

A model deciduous forest soil (Schaffenaker loamy sand) was treated for 8 mo in the greenhouse in 25 cm reconstructed columns with simulated throughfall at pH 6.0 or 4.0, and SO₄ ^2? levels of 12.8 or 24.8 mg L^?1. Red oak seedlings grown in the microcosms showed no growth or foliar element response to the treatments. Sulfate loading had a greater impact on soil and leachate chemistry than pH. Higher available soil P in the A, horizon was associated with the pH 6.0 and high SO₄ ^2?2 treatment combination. High SO₄ ^2? loading also reduced exchangeable K⁺ in the A_1?. Other soil horizons were unaffected by either treatment. Leachate chemistry was not significantly altered by througfall pH, but significantly greater export of Na⁺, Ca²⁺, Mg²⁺, Al³⁺, and NO₃ ^?, and lower SO₄ ^2? loss, occurred with low SO₄ ^? input. Comparatively half as much NO₃ ^? loss was associated with high SO₄ ^2? deposition. The high rate of NO₃ ^? leaching appeared responsible for greater equivalent mass loss of cations from the low SO₄ ^2? treatment. Leachate removal of SO₄ ^2? approximated input after 8 mo. The capacity of this soil to adsorb SO₄ ^2? appeared relatively limited in the absence of normal element cycling. The sulfate component of simulated deciduous forest throughfall was shown to have a potentially greater impact than pH on ion leaching from forest soil. Additional consideration of the role of SO^2? ₄ deposition, in the context of throughfall rather than incident precipitation, is warranted in studies of acidic deposition effects on internal forest soil processes.     

Sources of Nitrate in Snowmelt Discharge: Evidence From Water Chemistry and Stable Isotopes of Nitrate

To determine whether NO₃ ^? concentration pulses in surface water in early spring snowmelt discharge are due to atmospheric NO₃ ^?, we analyzed stream δ¹⁵N-NO₃ ^? and δ¹⁸O-NO₃ ^? values between February and June of 2001 and 2002 and compared them to those of throughfall, bulk precipitation, snow, and groundwater. Stream total Al, DOC and Si concentrations were used to indicate preferential water flow through the forest floor, mineral soil, and ground water. The study was conducted in a 135-ha subcatchment of the Arbutus Watershed in the Huntington Wildlife Forest in the Adirondack Region of New York State, U.S.A. Stream discharge in 2001 increased from 0.6 before to 32.4 mm day^?1 during snowmelt, and element concentrations increased from 33 to 71 μmol L^?1 for NO₃ ^?, 3 to 9 μmol L^?1 for total Al, and 330 to 570 μmol L^?1 for DOC. Discharge in 2002 was variable, with a maximum of 30 mm day^?1 during snowmelt. The highest NO₃ ^?, Al, and DOC concentrations were 52, 10, and 630 μmol L^?1, respectively, and dissolved Si decreased from 148 μmol L^?1 before to 96 μmol L^?1 during snowmelt. Values of δ¹⁵N and δ¹⁸O of NO₃ ^? in stream water were similar in both years. Stream water, atmospherically-derived solutions, and groundwaters had overlapping δ¹⁵N-NO₃ ^? values. In stream and ground water, δ¹⁸O-NO₃ ^? values ranged from +5.9 to +12.9‰ and were significantly lower than the +58.3 to +78.7‰ values in atmospheric solutions. Values of δ¹⁸O-NO₃ ^? indicating nitrification, increase in Al and DOC, and decrease in dissolved Si concentrations indicating water flow through the soil suggested a dilution of groundwater NO₃ ^? by increasing contributions of forest floor and mineral soil NO₃ ^? during snowmelt.     

Monitoring and Modeling Nitrate Persistence in a Shallow Aquifer

A modeling study on fertilizer by-products fate and transport was performed in an unconfined shallow aquifer equipped with a grid of 13 piezometers. The field site was located in a former agricultural field overlying a river paleochannel near Ferrara (Northern Italy), cultivated with cereals rotation until 2004 and then converted to park. Piezometers were installed in June 2007 and were monitored until June 2009 via pressure transducer data loggers to evaluate the temporal and spatial variation of groundwater heads, while an onsite meteorological station provided data for recharge rate calculations via unsaturated zone modeling. The groundwater composition in June 2007 exhibited elevated nitrate (NO ₃ ^? ) and chloride (Cl^?) concentrations due to fertilizer leaching from the top soil. The spatial distribution of NO ₃ ^? and Cl^? was heterogeneous and the concentration decreased during the monitoring period, with NO ₃ ^? attenuation (below 10?mg/l) after 650?days. A transient groundwater flow and contaminant transport model was calibrated versus observed heads and NO ₃ ^? and Cl^? concentrations. Cl^? was used as environmental tracer to quantify groundwater flow velocity and it was simulated as a conservative species. NO ₃ ^? was treated as a reactive species and denitrification was simulated with a first order degradation rate constant. Model calibration gave a low denitrification rate (2.5e^?3 mg-NO ₃ ^? /l/d) likely because of prevailing oxic conditions and low concentration of dissolved organic carbon. Scenario modeling was implemented with steady state and variable flow time discretization to identify the mechanism of NO ₃ ^? attenuation. It was shown that transient piezometric conditions did not exert a strong control on NO ₃ ^? clean up time, while transient recharge rate did, because it is the main source of unpolluted water in the domain.     

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.     

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).     

Nitrate reduction coupled with microbial oxidation of sulfide in river sediment

Purpose

Nitrate (NO ₃ ^? ) is often considered to be removed mainly through microbial respiratory denitrification coupled with carbon oxidation. Alternatively, NO ₃ ^? may be reduced by chemolithoautotrophic bacteria using sulfide as an electron donor. The aim of this study was to quantify the NO ₃ ^? reduction process with sulfide oxidation under different NO ₃ ^? input concentrations in river sediment.

Materials and methods

Under NO ₃ ^? input concentrations of 0.2 to 30?mM, flow-through reactors filled with river sediment from the Pearl River, China, were used to measure the processes of potential NO ₃ ^? reduction and sulfate (SO ₄ ^2? ) production. Molecular biology analyses were conducted to study the microbial mechanisms involved.

Results and discussion

Simultaneous NO₃ ^? removal and SO₄ ^2? production were observed with the different NO ₃ ^? concentrations in the sediment samples collected at different depths. Potentially, NO ₃ ^? removal reached 72 to 91?% and SO ₄ ^2? production rates ranged from 0.196 to 0.903?mM?h^?1. The potential NO ₃ ^? removal rates were linearly correlated to the NO ₃ ^? input concentrations. While the SO ₄ ^2? production process became stable, the NO ₃ ^? reduction process was still a first-order reaction within the range of NO ₃ ^? input concentrations. With low NO ₃ ^? input concentrations, the NO ₃ ^? removal was mainly through the pathway of dissimilatory NO ₃ ^? reduction to NH ₄ ⁺ , while with higher NO ₃ ^? concentrations the NO ₃ ^? removal was through the denitrification pathway.

Conclusions

While most of NO ₃ ^? in the sediment was reduced by denitrifying heterotrophs, sulfide-driven NO ₃ ^? reduction accounted for up to 26?% of the total NO ₃ ^? removal under lower NO ₃ ^? concentrations. The vertical distributions of NO ₃ ^? reduction and SO ₄ ^2? production processes were different because of the variable bacterial communities with depth.     

Bulk Atmospheric Deposition in the Southern Po Valley (Northern Italy)

A study on pH and chemical composition of precipitation was carried out in two Italian sites, one urban (site 1) and one rural (site 2), located approximately 30 km far from Bologna, during a 3-year period. No significative site variation was found. In both locations, bulk deposition pH ranged from slightly acid to slightly alkaline, despite the volume weighted mean concentration of acidic species, NO ₃ ^? and SO ₄ ^2? (67.4 and 118.4 μeq l^?1 in site 1 and 88.7 and 103.8 μeq l^?1 in site 2), that were similar to those of typical acidic rainfall region. This might be ascribed to the neutralization reaction of the Ca²⁺, attributed to the calcareous soil and the frequent dusty air mass intrusion from the Sahara. The pair correlation matrix and the analysis of the main components suggested also ammonium and other crustal elements as neutralization agents. The depositional rate of SO ₄ ^2? and NO ₃ ^? , chemical elements of agricultural interest, amounted to 38 and 28 and 32 and 35 kg ha^?1 for site 1 and site 2, respectively. These supplies of nutrient were not negligible and had to be considered on cultivated lands. NH ₄ ⁺ deposition rate on site 2 was 7 kg ha^?1, 23% over site 1, probably due to nitrogen fertilization in the fields around the monitoring station. In site 1, SO ₄ ^2? presented a seasonal trend, indicating that its principal source was the residential heating. Results emphasized that the entity of the bulk deposition acidification is linked not only to the ions local emission sources (fossil fuel combustions, heating, and fertilizers) but also to the surrounding territory and the prevalent wind that transports through kilometers air masses which may contain acidic and alkaline species.     

Long-term sulfate dynamics at lange bramke (Harz) used for testing two acidification models

At Lange Bramke (Harz) soil solution and runoff concentrations of major elements were observed over 16 yr. During this period acid deposition was high but showed a marked decrease of H⁺ and SO ₄ ^2? both in concentrations and fluxes over the last five years. Among others, this record reveals the following patterns: seasonality in the signals for SO ₄ ^2? and NO ₃ ^? in runoff which are synchronous; an accumulation of SO ₄ ^2? in the soil, initially up to 50% of the deposition fluxes; apparently no correlation between runoff and SO ₄ ^2? concentration, and no long-term trend in runoff concentration of SO ₄ ^2? . In this paper we use these patterns in the data set from Lange Bramke to test two established acidification models. The test criterion is that the algorithms employed by the SO ₄ ^2? modules of these models must be able to reproduce these features. To that end, both models need not to be run as it can be shown that even with completely unrestricted parameter values the two algorithms are unable to match the observed SO ₄ ^2? dynamics. The MAGIC model (Cosbyet al., 1985) is unable to reproduce, given the existence of net SO ₄ ^2? accumulation, the constant SO ₄ ^2? concentration in runoff during the last 16 years. The second model, BEM (Prenzel, 1986), is succesful in reconstructing the constant SC>4~ levels in runoff. However, on a monthly time scale BEM predicts a shift between the periodic maximum concentrations of SO ₄ ^2? and NO ₃ ^? which is not observed in the data.