An Automated Wet Deposition System to Compare the Effects of Reduced and Oxidised N on Ombrotrophic Bog Species: Practical Considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^–1 y^–1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of real world treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below4mMin rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^–1 y^–1 adjusted for ambient deposition (8 kg N ha^–1 y^–1). The 16 and 64 kg N ha^–1 y^–1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^–1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^–1 at 3.0 g m^–3 to 30 s m^–1 at 30 g m^–3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

A Chronology of Nitrogen Deposition in the UK Between 1900 and 2000

Measurements of the concentrations of nitrogen compounds in air and precipitation in the UK have been made since the mid-19th century, but no networks operating to common protocols and having traceable analytical procedures were established until the 1950s. From 1986 onwards, a high-quality network of sampling stations for precipitation chemistry was established across the UK. In the following decade, monitoring networks provided measurement of NO₂, NH₃, HNO₃ and a satisfactory understanding of the dry deposition process for these gases allowed dry deposition to be quantified. Maps of N deposition for oxidized and reduced compounds at a spatial scale of 5 km × 5 km are available from 1986 to 2000. Between 1950 and 1985, the more limited measurements, beginning with those of the European Air Chemistry Network (EACN) provide a reasonable basis to estimate wet deposition of NO ₃ ^– –N and NH ₄ ⁺ –N. For the first half of the century, estimates of deposition were scaled with emissions assuming a constant relationship between emission and deposition for each of the components of the wet and dry deposition budget at the country scale. Emissions of oxidized N, which dominated total nitrogen emissions throughout the century, increased from 312 kt N annually in 1900 to a peak of 787 kt for the decade 1980–1990 and then declined to 460 kt in 2000. Emissions of reduced N, largely from coal combustion were about 168 kt N in 1900, increasing to a peak of 263 kt N in 2000 and by now dominated by agricultural sources. Reduced N dominated the deposition budget at the country scale, increasing from 163 kt N in 1900 to 211 kt N in 2000, while deposition of oxidized N was 66 kt N in 1900 and 191 kt N in 2000. Over the century, 68 Mt (Tg) of fixed N was emitted within the UK, 78% as NO _x , while 29 Mt of nitrogen was deposited (43% of emissions), equivalent to 1.2 t N ha^–1, on average, with 60% in the reduced form. Deposition to semi-natural ecosystems is approximately 15 Tg N, equivalent to between 1 and 5 t N ha^–1, over the century and appears to be accumulating in soil. The N deposition over the century is similar in magnitude to the total soil N inventory in surface horizons.     

The Influence of Atmospheric N Deposition on Nitrous Oxide and Nitric Oxide Fluxes and Soil Ammonium and Nitrate Concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO ₃ ^– and NH ₄ ⁺ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH ₄ ⁺ and NO ₃ ^– concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH ₄ ⁺ and NO ₃ ^– in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH ₄ ⁺ , but the relationship between NH ₄ ⁺ and N deposition (ln NH ₄ ⁺ = 0.62 ln N_deposition + 0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

Study of Bulk and Sub-Event Wet Deposition in Gebze,Turkey

This study presents the chemical composition of bulk deposition during the period of February 1996–May 1997 and the chemical composition of sub-event wet deposition on 13 August 1997 in Gebze. Samples were analyzed for SO₄ ^2-, NO₃ ^-, Cl^-,Ca²⁺, Mg²⁺, K⁺, Na⁺, and NH₄ ⁺ in addition to pH. The source of some ionic components in the bulk deposition such as K⁺ and Ca²⁺ were found to be the terrestrial regions, as expected. The (non-sea Cl^-)/Cl^- ratio of 0.05 suggests that the very large portion of Cl^- in the bulkdeposition was of marine origin. The ratio of (non-sea SO₄ ^2-)/SO₄ ^2- varied between 0.86 and 0.99,indicating that the main source of sulfate was not the sea. It is found that the sulfate and calcium concentrations were highest in summer and lowest in fall. The analysis of bulk deposition also indicated that nearly 24% of the events were acidic (pH < 5.6). During sub-event wet deposition collectedon the same site pH decreased continually, and during the passageof cold front concentrations of Cl^-, SO₄ ^2- and NO₃ ^- increased.     

Early Effects of Atmospheric Ammonia Deposition on Calluna Vulgaris (L.) Hull Growing on an Ombrotrophic Peat Bog

This paper reports data from a field study investigating the impacts of elevated ammonia (NH₃) deposition on Calluna vulgaris growing on an ombrotrophic peat bog in S.E. Scotland. Shoot extension, foliar N concentrations, chlorophyll concentration and chlorophyll fluorescence were measured during the second growing season of exposure to a gradient of ammonia concentrations. Results indicate that NH₃ increases growth between 150–200 kg N ha^–1y^–1 cumulative deposition. Foliar N content increased significantly in response to NH₃ cumulative deposition up to 400 kg N ha^–1 y^–1 whereas chlorophyll a content significantly decreased. Measurements of Fv/Fm suggest that although NH₃ exposure altered the growth and reduced chlorophyll a, the efficiency of photosystem II was insensitive to NH₃-N deposition at this stage.     

Oxidation of SO2 in Clouds at Whiteface Mountain

In-cloud oxidation of SO₂ byH₂O₂ was investigated using a tracertechnique based on SO^2– ₄/Se ratios atWhiteface Mountain, New York during summer months from1990 to 1998. Cloud water samples collected at themountain's summit (1.5 km above mean sea level) andaerosols at a below cloud site (Lodge) located at 0.6km amsl and in cloud interstitial air at the summitwere analyzed for SO^2– ₄ and selectedtrace elements. Gaseous SO₂ andH₂O₂were measured in realtime. Cloud water pH wasgenerally below 5.0 with a mean value of 3.6. Theresults show that significant in cloud oxidation occursin clouds during summer months varying from belowdetection to 62% with on average approximately 24% ofthe cloud water SO^2– ₄ produced from in-situ SO₂ oxidation. During summer the clouds wereoxidant limited for approximately one third of thetime.     

A case study of microwave processing of metal hydroxide sediment sludge from printed circuit board manufacturing wash water

The large quantity of wash water used in the electroplating and etching process in the manufacturing of printed circuit boards (PCBs) contains a high level of heavy metal ions (Cu⁺⁺, Zn⁺⁺, Ni⁺⁺, Cr⁺⁺⁺, Pb⁺⁺). These potentially toxic ions are removed from the wash water effluent through a polyelectrolyte flocculation and hydroxide precipitation process during which a hydroxide sediment sludge rich in metal ions and polymers is generated. This sediment sludge possesses some unique characteristics and properties in terms of composition, fine particle size distribution, high specific surface area, and a tendency to agglomerate after drying. Direct disposal of this classified “special waste” (Department of Environment of Northern Ireland, The Special Waste Regulations, Northern Ireland, 1998) at landfill sites may cause serious soil and underground water pollution through a gradual ionic leaching process. This paper describes an experimental investigation, exploratory in nature, which employs microwave radiation for detoxification of the sediment sludge through microwave heating, drying and metal ion immobilization within the sediment solids. The effectiveness of microwave assisted binding and immobilization of the metal ions within the sediment solids was studied in conjunction with an evaluation of microwave energy efficiency in comparison to the more conventional convective heating and drying processes. Given a sufficient amount of microwave radiation, leaching of Cu²⁺ and Pb²⁺ was reduced by 2700% and 1080%, respectively, over a period of 12 weeks, and further leaching was not detectable within six months at simulated local landfill aqueous conditions. This paper also attempts, through experimental observation, to add to the very limited understanding of the complex interactions and binding of free metal ions with the polymeric materials and metal hydroxides under the influence of an electromagnetic field. The high specific surface of the sediment solids and their adsorption properties were further explored and characterized in a study of adsorption of reactive dyes by the microwave processed solids.     

Controls on Leaching of N Species in Upland Moorland Catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^–1 yr^–1, respectively. TheNH ₄ ⁺ leaching appears to be predominantly regulated by flowpath in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherowand Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO ₃ ^– also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO ₃ ^– concentrations are associated with tributaries draining soils contributingwater with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH ₄ ⁺ inputs and leaching losses of inorganic N throughout the year.     

Trends in Water Chemistry in a Maple Forest on a Steep Slope

Year-to-year variation in SO₄ ^2-,NO₃ ^-, Ca²⁺, K⁺, and Mg²⁺concentrations in forest floor and mineral soil percolatefrom a forested, podzolic soil at the Turkey Lakes Watershedon the Precambrian Shield was assessed for monotonic trendsbetween 1986 and 1995. Our objective was to examine howrapidly ion concentrations in soil percolate equilibratedafter stabilization of SO₄ ^2- concentrations inprecipitation. Significant negative trends were detected inmonthly Ca²⁺, and Mg²⁺ concentrations in forestfloor and SO₄ ^2-, Ca²⁺, and Mg²⁺ inmineral soil percolate during the 10-year-period. Thedecline in Ca²⁺ and Mg²⁺ was greater than annualdecreases in SO₄ ^2- and NO₃ ^- in forestfloor percolate and proportional to the reduction inSO₄ ^2- in mineral soil percolate. Response ofmineral soil percolate to a 15 mol_c L^-1SO₄ ^2- decrease in wet-only precipitation between1985 and 1986 was a gradual decline in SO₄ ^2-concentration through 1995. The five-year meanSO₄ ^2- concentration in bulk precipitation, forestfloor percolate, and mineral soil percolate decreased 8, 9and 18 mol_c L^-1 from 1986–90 to 1991–95.Microbial (mineralization of organic S) and sorption(release from and/or retention in the pool of insolubleSO₄ ^2-) processes in the soil were logicalexplanations for the observed changes in SO₄ ^2- inmineral soil percolate.     

Organic Nitrogen in Precipitation Across the United Kingdom

The concentration of water-soluble organic nitrogen (WSON) in precipitation has been measured at seven sites across the United Kingdom, over a period of 1–2 years, using protocols developed in a pilot study. Samples were collected over 1–2 weeks in continuously open funnels made of stainless steel, draining to a glass bottle, and were preserved during and after collection by the addition of thymol. After chemical analysis, samples were excluded from the long-term average if they showed signs of contamination (significant concentrations of K⁺ or PO₄ ^3–). Two methods of measuring total dissolved N were used, persulphate oxidation and high-temperature chemiluminescence. The latter generally gave the larger values, and has been used to asses the organic component of dissolved N. The long-term data set confirms the original results from the pilot study - organic N contributes between 24 and 40% to the total annual wet deposition of dissolved N across the United Kingdom. The fraction of WSON was greatest at western sites, and was strongly correlated with ammonium concentrations. However, the seasonal pattern across all sites showed a late spring maximum for ammonium and nitrate, but a late summer maximum for WSON. The magnitude of the contribution of WSON to wet-deposited N has implications for the setting and assessment of critical loads for N deposition.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^?1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^?1 at 3.0 μg m^?3 to 30 s m^?1 at 30 μg m^?3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

The Spatial and Temporal Variation of Measured Urban PM10 and PM2.5 in the Helsinki Metropolitan Area

We have studied particulate matter (PM) concentrations,PM₁₀ and PM_2.5, measured in an urban air qualitymonitoring network in the Helsinki Metropolitan Area during1997–1999. The data includes PM₁₀ concentrationsmeasured at five locations (two urban traffic, one suburbantraffic, one urban background and one regional backgroundsite) and PM_2.5 concentrations measured at twolocations (urban traffic and urban background sites). Theconcentrations of PM₁₀ show a clear diurnal variation,as well as a spatial variation within the area. Bycontrast, both the spatial and temporal variation of thePM_2.5 concentrations was moderate. We have analysedthe evolution of urban PM concentrations in terms of therelevant meteorological parameters in the course of oneselected peak pollution episode during 21–31 March, 1998.The meteorological variables considered included wind speedand direction, ambient temperature, precipitation, relativehumidity, atmospheric pressure at the ground level,atmospheric stability and mixing height. The elevated PMconcentrations during the 1998 March episode were clearlyrelated to conditions of high atmospheric pressure,relatively low ambient temperatures and low wind speeds inpredominantly stable atmospheric conditions. The resultsprovide indirect evidence indicating that the PM₁₀concentrations originate mainly from local vehiculartraffic (direct emissions and resuspension), while thePM_2.5 concentrations are mostly of regionally andlong-range transported origin.     

Neutralisation of Sulphur Dioxide Deposition in a Coniferous Canopy

Previously, it has been observed that the internal circulation (ion leakage) of calcium from a coniferous forest is caused by uptake of sulphur dioxide (SO₂). Here we show that this correlation was not changed when the forest floor is covered with a roof. The reaction takes place in the canopy and is not influenced by deposition and root uptake of calcium and sulphate. The ion leakage of calcium is linked to the loss of acidity in throughfall. The process can, for one of the catchments, schematically be written: SO₂ + H₂O + 0.5 O₂ + 0.58 CaA₂→ SO₄ ^2- + 0.94 H⁺ + 0.58 Ca²⁺ + 1.16 HA, in which A denotes the anion to a weak acid. This reaction also takes place today when the SO₂ concentration is very low, but when the precipitation is still acidic. The ion leakage of manganese also is caused by the uptake of SO₂, but only 0.12 manganese ions are released per SO₂ molecule.     

Implications of Heterogeneous Chemistry of Nitric Acid for Nitrogen Deposition to Marine Ecosystems: Observations and Modeling

Size resolved particle composition and nitric acid (HNO₃)measurements from the ASEPS'98 experiment conducted in the BalticSea are used to provide observational evidence of substantialgas-particle transfer of oxidized nitrogen (N) compounds in themarine boundary layer. We then focus on the importance ofHNO₃ reactions on sea salt particles in determining spatio-temporal patterns of N dry deposition to marine ecosystems.Modelling results obtained assuming no kinetic or chemical limiton HNO₃ uptake and horizontally homogeneous conditions withnear-neutral stability, indicate that for wind speeds 3.5 – 10 ms^-1 transfer of HNO₃ to the particle phase to formparticle nitrate (NO₃ ^-) may decrease the N depositionvelocity by 50%. We extend this research using the CHEM-COASTmodel to demonstrate that, in a sulphur poor environment undermoderate wind speeds with HNO₃ concentrations representativeof those found in the marine boundary layer, inclusion ofheterogeneous reactions on sea spray significantly reducesmodelled NO₃ ^- deposition in the near coastal zone.     

The influence of atmospheric n deposition on nitrous oxide and nitric oxide fluxes and soil ammonium and nitrate concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO^? ₃ and NH⁺ ₄ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH⁺ ₄ and NO^? ₃ concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH⁺ ₄and NO^? ₃ in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH⁺ ₄, but the relationship between NH⁺ ₄ and N deposition (ln NH⁺ ₄ = 0.62 ln N_deposition+0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

Chemical Composition and Acidity of Rain at the Gulf of Iskenderun,North-East Mediterranean

The purpose of the present work was to investigate the chemistry of rain in the Gulf of Iskenderun, North East Mediterranean, Turkey. The Gulf region has a large number of industries. Main industries existing in the region are iron and steel works, fertilizer plants, a cement plant, and several medium and mini size steel mills in addition to the international pipe line terminals. This study aims to apportion the local sources contributing to the overall pollution of the region. To this end a precipitation sampling program was started in January 2000, and over 48 precipitation samples were collected from each of 5 stations located at Iskenderun city center, Iskenderun industrial zone, Payas city center, the campus of Iskenderun Technical College and the campus of Mustafa Kemal University. Samples were analysed for pH, NO₃ ⁺, Cl^-. Ca, Al, Ba, Na, Cd, Co, Cr, Cu, Pb, Li, Mg, Mn, Ni, Zn, Fe, K. Concentrations of metal ions were determined by ICP-AES. NO₃ ^- ions and pH were determined by using NO₃ ^- selective electrode and pH meter, respectively.pH values of the collected samples at the industrial zone and at Payas city center, ranged between 5.02 and 7.38, respectively. NO₃ ^- and metal ions concentrations were highly variable. Concentrations of Ca and Fe ions were higher in the industrial zone and Payas city center. In the other three stations, concentrations of metal ions and NO₃ ^- ion were lower than that of industrial zone and the values of pH ranged between 6 and 7.4. The average pH values at Iskenderun Gulf showed that the precipitation was not acidic, because of the high concentration of Ca. The highest concentrations of Na and Cl ions were recorded in the University campus because the campus is located by the Mediterranean Sea.     

Modelling of Air Quality with CAMx: A Case Study in Switzerland

The three-dimensional Eulerian model CAMx (Comprehensive Air QualityModel with Extensions) was applied for the first time to simulate bothgaseous and particulate photochemical air pollution in Switzerland during July 28–30, 1993. The meteorological input data were prepared using the Systems Applications International Mesoscale Model (SAIMM). The CAMx model results were compared with the measurements carried out at ground level andfrom airborne measuring platforms within the frame of the Swiss POLLUMET research programme. In general, the CAMx performance for gaseous species wasfound to be better than that of the previously used Urban Airshed Model (UAM)and the Variable Grid Urban Airshed Model (UAM-V). The most significant improvement for the gaseous species is in the prediction of HNO₃ concentrations, due to the inclusion of aerosol chemistry. Aerosol species such as NO₃ ^-, NH₄ ⁺, SO₄ ^2-, and secondary organic aerosols were calculated in one particle size range (0.04–2.5 m) and compared with a few measurements available. Although July 29 was reasonably well simulated, overestimated wind speeds by SAIMM for July 30 caused a too fast transport of pollutants. Similarly to measurements, significant spatial correlation of the secondarily formed aerosols with ozone and formaldehyde is found in the afternoon.     

Acid Rain in Downtown São Paulo City, Brazil

During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown São Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, $ \rm NH^{ + }_{4} During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown S?o Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, , K⁺, Ca²⁺, Mg²⁺, Cl⁻, , ) and carboxylic acids (acetic, formic and oxalic) using ion chromatography. The volume weighted mean, VWM, of the anions , and Cl⁻ was, respectively, 20.3, 12.1 and 10.7 μmol l⁻¹. Rainwater in S?o Paulo was acidic, with 55% of the samples exhibiting a pH below 5.6. The VWM of the free H⁺ was 6.27 μmol l⁻¹), corresponding to a pH of 5.20. Ammonia (NH₃), determined as (VWM = 32.8 μmol l⁻¹), was the main acidity neutralizing agent. Considering that the H⁺ ion is the only counter ion produced from the non-sea-salt fraction of the dissociated anions, the contribution of each anion to the free acidity potential has the following profile: (31.1%), (26.0%), CH₃COO⁻ (22.0%), Cl⁻ (13.7%), HCOO⁻ (5.4%) and (1.8%). The precipitation chemistry showed seasonal differences, with higher concentrations of ammonium and calcium during autumn and winter (dry period). The marine contribution was not significant, while the direct vehicular emission showed to be relevant in the ionic composition of precipitation.     

Fate of saline ions in a planted landfill site with leachate recirculation

Recirculation of leachate on a covered landfill site planted with willows or other highly evapotranspirative woody plants is an inexpensive option for leachate management. In our study, a closed landfill leachate recirculation system was established on a rehabilitated municipal solid waste landfill site with planted landfill cover. The main objective of the study was to evaluate the sustainability of the system with regard to high hydraulic loads of the landfill leachate on the landfill cover and high concentrations of saline ions, especially potassium (K⁺), sodium (Na⁺) and chloride (Cl^?), in leachate.The results of intensive monitoring, implemented during May 2004 and September 2007, including leachate, soil and plant samples, showed a high sustainability of the system regarding saline ions with the precipitation regime of the studied region. Saline ion concentrations in leachates varied between 132 and 2592 mg Cl^? L^?1, 69 and 1310 mg Na⁺ L^?1 and between 66 and 2156 mg K⁺ L^?1, with mean values of 1010, 632 and 686 mg L^?1, respectively. Soil salinity, measured as soil electrical conductivity (EC), remained between 0.17 and 0.38 mS cm^?1 at a depth between 0 and 90 cm. An average annual precipitation of 1000 mm provided sufficient leaching of saline ions, loaded by irrigation with landfill leachate, from the soil of the landfill cover and thus prevented possible salinity shocks to the planted willows.