The use of silver as a selective precipitant for I in radioactive waste management

¹²⁹I is one of the more hazardous nuclides occurring in radioactive waste. In the form of I⁻, its most likely speciation, it is poorly sorbed on most geologic media. Several workers have suggested the use of silver to precipitate I⁻ as the insoluble AgI, in a cemented waste form, or as a “getter”. The efficacy of this procedure is examined by experiment, in conjunction with thermodynamic predictions.The addition of AgNO₃ to Portland cement leads to coprecipitation with C-S-H, with low Ag solubilities ( 10 μmg/L); 2–;3 orders of magnitude lower than predicted (from Ag₂O). AgI is stable in these matrices, with low aqueous I concentrations (<2 mg/L). In 85% BFS-15% OPC pastes, AgI is unstable due to redox and complexation reactions, with much I⁻ passing into solution; concentrations up to 900 mg/L were observed. It is shown that repository conditions, on closure, are also likely to induce solubilisation of I⁻ from AgI. It is concluded that the use of Ag is unlikely to significantly improve the immobilisation properties of the near field for radioiodine.     

Petroliferous wastewaters treatment with water hyacinths (Raffinerie de Provence, France): Experimental statement

The production and purification abilities of the water hyacinth, Eichhornia crassipes (Mart.) Solms., were tested on petrochemical wastewaters at Raffinerie de Provence, Total (La Mède, France), in controlled and in situ experiments. The mean production obtained was of about 6.1 g (dry weight) day⁻¹ m⁻² (10-fold lower than those obtained on paper industry effluent), and can be explained by the high salinity and pH of the effluent, and the negative effect of hydrocarbons. In comparison with the control pond, the water hyacinth system induced a rapid settlement effect. Finally, the removal gains due to the water hyacinths system were about 26% for the suspended solids (i.e. 40.1 kg day⁻¹), 28% for the total hydrocarbons (i.e. 17.2 kg day⁻¹) and 18% for the total organic carbon (i.e. 27 kg day⁻¹).     

Biosorptive removal of Pb(II) and Cu(II) from wastewater using activated carbon from cassava peels

The ability of activated carbon from cassava peels to remove heavy metals like Cu(II) and Pb(II) from hospital wastewater was investigated. The study showed that a pH of 8 was the best for the sorption of both metal ions onto the biosorbent. The time-dependent experiments for the metal ions showed that the binding of the metal ions to the biomass was rapid and occurred within 20–120 min. Sorption efficiency increased with a rise in adsorbent dosage. It increased from 12 to 73 % for Pb(II) and 26 to 79 % for Cu(II) when the adsorbent dose increased from 2 to 12 g. An increase in temperature led to an increase in sorption for both metal ions. The Langmuir model showed that the biomass has a higher sorption capacity for Cu(II) than Pb(II), with q _m = 5.80 mg g^?1 for Pb(II) and 8.00 mg g^?1 for Cu(II). The Freundlich isotherm K _f was 1.4 for Pb(II) and 1.8 for Cu(II), indicating a preferential sorption of Cu(II) onto the biosorbent. Adsorption capacity was found to decrease with an increase in particle sizes. Sorption occurred by physical mechanisms and was mainly controlled by intraparticle diffusion.     

Geochemistry of Iron and Sulfur in the Zone of Microbial Sulfate Reduction in Mine Tailings

The cycling of iron and sulfur in mine tailings depends on various chemical and microbial reactions. The present study was undertaken in order to assess the role played by populations of sulfate-reducing bacteria (SRB) on the fate of Fe and SO₄ ^2- in Cu–Zn and Au tailings. Samples were taken along a 50-cm deep profile at all sites and analyzed for SRB populations, solid-phase mineralogy and porewater geochemistry. Results indicated that the Cu–Zn tailings were highly oxidized near the surface, as shown by the very low pH, high redox potential, large concentrations of soluble Cu, Zn and sulfate in the porewaters, and the depletion of pyrite. On the other hand, Au tailings were more pH neutral, slightly anoxic, and showed low concentrations of Fe and SO₄ ^2- in the porewaters and very little pyrite oxidation. SRB populations in the Cu–Zn tailings increased with depth, just below the oxic/anoxic interface and were linked to a decline of sulfate and DOC concentrations around the same depths. However, large concentrations of dissolved Fe were also observed around the same depth intervals. Our results suggest that SRB could be involved in sulfate reduction in the Cu–Zn tailings, because the solubility of sulfate was not controlled by the precipitation of sulfate-rich minerals. However, the presence of soluble Fe in the reduced portion of the tailings was also indicative of the presence of iron reducing bacteria (IRB). These bacteria were not enumerated in the present study, but their co-occurrence with SRB has been reported in the past in similar mining environments. The decline of sulfate and the release of soluble iron into the porewaters were also paralleled by a pH increase and the generation of alkalinity. In the Au tailings, SRB populations were generally constant throughout the depth profile and could not be ascribed to sulfate reduction in the porewaters. The solubilities of sulfate and iron in these tailings were partially controlled by jarosite and Fe-oxide minerals. It is then clear that SRB populations could be recovered from various mining sites, but their activity cannot be ascertained based on microbial enumeration and geochemical data.     

Short term effects of copper, sulfadiazine and difloxacin on the anaerobic digestion of pig manure at low organic loading rates

Antibiotics of inorganic and organic origin in pig manure can inhibit the anaerobic process in biogas plants. The influence of three frequently used antibiotics, copper dosed as CuSO₄, sulfadiazine (SDZ), and difloxacin (DIF), on the anaerobic digestion process of pig manure was studied in semi-continuous experiments. Biogas production recovered after every Cu dosage up to a sum of 12.94 g Cu kg⁻¹ organic dry matter (ODM), probably due to Cu precipitation following the formation of sulphide from sulphate. Complete inhibition was found at the very high Cu concentration of 19.40 g Cu kg⁻¹ ODM. Inhibitory effect of SDZ and DIF was observed at concentrations as high as 2.70 g kg⁻¹ ODM and 0.54 g kg⁻¹ ODM, respectively. It seems very unlikely that the antibiotics tested would inhibit the anaerobic process in a full-scale biogas plant.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation

Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH₄) emission resulting from rice cultivation. In laboratory incubations, CH₄ production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt⁻¹), while observed CO₂ production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH₄ emission rates from the rice planted potted soils significantly decreased with the increasing levels (2–20 Mg ha⁻¹) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha⁻¹ application level of the amendments, total seasonal CH₄ emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH₄ production rates as well as total seasonal CH₄ flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens’ activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH₄ emissions as well as sustaining rice productivity.     

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.     

Artificial carbonation for controlling the mobility of critical elements in bottom ash

In municipal solid waste incineration (MSWI), bottom ash, generated at a stoker grate type incinerator, the critical elements were identified in terms of EU regulation. The stabilizing effect of moderate carbonation (pH 8.28 ± 0.03) on critical contaminants was studied through availability and diffusion leaching protocols. Data from the performed tests were evaluated with the goal of reusing MSWI bottom ash as secondary construction material. To investigate the mobilizing effect of CO₂, suspended MSWI bottom ash was severely carbonated (pH 6.40 ± 0.07). The effect of CO₂ and its interaction with other leaching factors, such as liquid/solid (L/S) ratio, leaching time, pH, ultrasound treatment, and leaching temperature, were examined using a reduced 2^6-1 experimental design. Contaminants identified as critical were Cr, Cu, Mo, Sb, Cl⁻, and SO₄ ²⁻. Although moderate carbonation decreased the release of Cr, Cu, Mo, and Sb from compacted bottom ash, the main disadvantage remains its inability to demobilize Cl⁻ and SO₄ ²⁻. The hypothesized mobilizing effect of severe carbonation was proven. The treatment enhanced the separation of critical components (α = 0.05) (except for Cl⁻), i.e., about fivefold for Sb and about twofold for Cr, Cu, and S. Nevertheless, the prospect is good that severe carbonation could constitute the deciding key parameter to facilitate the technical feasibility of a future washing process for MSWI bottom ash.     

Monitoring Studies of Precipitation and Cap Cloud Chemistry at Holme Moss in the Southern Pennines

Weekly collections of samples of precipitation and hill cloudwater have been made at Holme Moss (530 m.a.s.l.) in the southernPennines covering a six-year period (1994–1999). In addition continuous meteorological measurements have been conducted at thesite for a five year period (1995–1999). The concentrations of major ions in the samples have been determined by ion chromatography. Analysis of ion concentrations as a function ofwind direction reveals that the ions with anthropogenic sources (SO₄ ^–, NO₃ ^–, NH₄ ⁺, H⁺) exhibit higher concentrations during easterly wind directions whilst the ions with predominantly marine origins (Na⁺, Cl^–, Ca⁺⁺, Mg⁺⁺, K⁺) have concentrations thatare not significantly dependant on wind direction. Precipitation and cloud deposition are strongly correlated to south-westerly wind directions with a secondary peak occurring for north-easterly directions. Fifty nine per cent of ion deposition by rain was found to occur during wind from the SSW to W sector.The average concentrations of ions in cloud water were found tobe much higher than those in rain (by factors of between 2.5 and4.2). It is thought that the high precipitation and annual deposition of ions by precipitation at Holme Moss is due in partto the enrichment of ion concentrations in precipitation by thescavenging of more concentrated cap cloud droplets (the `seeder-feeder effect'). Comparison with data from a nearby lower level site shows encouraging agreement with the scheme currently used in the U.K. deposition mapping procedure to incorporate the influence of orography on deposition by precipitation.     

Application of response surface methodology to the advanced treatment of biologically stabilized landfill leachate using Fenton’s reagent

A Fenton process that uses FeCl₂ as the alternative catalyst was employed to deal with the biologically treated landfill leachate. Data obtained revealed that this Fenton process can provide an equivalent pollutant removal as the Fenton process that uses FeSO₄ as catalyst. Central composite design (CCD) and response surface methodology (RSM) were applied to evaluate and optimize the four key factors, namely initial pH, Fe(II) dosage ([Fe²⁺]), H₂O₂/Fe(II) mole ratio ([H₂O₂]/[Fe²⁺] ratio) and reaction time, which affect the performance of the Fenton treatment. Chemical oxygen demand (COD) and color were selected as response variables. This approach provided statistically significant quadratic models, which were adequate to predict responses and to carry out optimization under the conditions studied. It was demonstrated that the interaction between initial pH and [H₂O₂]/[Fe²⁺] ratio has a significant effect on the COD removal, while the interaction between [H₂O₂]/[Fe²⁺] ratio and reaction time shows a large impact on color removal. The optimal conditions were found to be initial pH 5.9, [Fe²⁺] = 9.60 mmol/L, [H₂O₂]/[Fe²⁺] ratio = 2.38, reaction time = 5.52 h. Under this optimal scheme, the COD and color in the effluent were reduced to 159 mg/L and 25°, respectively, with an increase of BOD₅/COD ratio from 0.05 to 0.21.     

A methodology to determine gaseous emissions in a composting plant

Environmental impacts associated to different waste treatments are of interest in the decision-making process at local, regional and international level. However, all the environmental burdens of an organic waste biological treatment are not always considered. Real data on gaseous emissions released from full-scale composting plants are difficult to obtain. These emissions are related to the composting technology and waste characteristics and therefore, an exhaustive sampling campaign is necessary to obtain representative and reliable data of a single plant. This work proposes a methodology to systematically determine gaseous emissions of a composting plant and presents the results obtained in the application of this methodology to a plant treating source-separated organic fraction of municipal solid waste (OFMSW) for the determination of ammonia and total volatile organic compounds (VOC). Emission factors from the biological treatment process obtained for ammonia and VOC were 3.9 kg Mg OFMSW⁻¹ and 0.206 kg Mg OFMSW⁻¹ respectively. Emissions associated to energy use and production were also quantified (60.5 kg CO₂ Mg OFMSW⁻¹ and 0.66 kg VOC Mg OFMSW⁻¹). Other relevant parameters such as energy and water consumption and amount of rejected waste were also determined. A new functional unit is presented to relate emission factors to the biodegradation efficiency of the composting process and consists in the reduction of the Respiration Index of the treated material. Using this new functional unit, the atmospheric emissions released from a composting plant are directly related to the plant specific efficiency.     

Comparison of different liquid anaerobic digestion effluents as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover

Effluents from three liquid anaerobic digesters, fed with municipal sewage sludge, food waste, or dairy waste, were evaluated as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover in mesophilic reactors. Three feedstock-to-effluent (F/E) ratios (i.e., 2, 4, and 6) were tested for each effluent. At an F/E ratio of 2, the reactor inoculated by dairy waste effluent achieved the highest methane yield of 238.5 L/kgVS_feed, while at an F/E ratio of 4, the reactor inoculated by food waste effluent achieved the highest methane yield of 199.6 L/kgVS_feed. The microbial population and chemical composition of the three effluents were substantially different. Food waste effluent had the largest population of acetoclastic methanogens, while dairy waste effluent had the largest populations of cellulolytic and xylanolytic bacteria. Dairy waste also had the highest C/N ratio of 8.5 and the highest alkalinity of 19.3 g CaCO₃/kg. The performance of solid-state batch anaerobic digestion reactors was closely related to the microbial status in the liquid anaerobic digestion effluents.     

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.     

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.     

Anaerobic treatment of effluents from an industrial polymers synthesis plant

The feasibility of the anaerobic treatment of an industrial polymer synthesis plant effluent was evaluated. The composition of the wastewater includes acrylates, styrene, detergents, a minor amount of silicates and a significant amount of ferric chloride. The average chemical oxygen demand (COD) corresponding is about 2000 mg/l. The anaerobic biodegradability of the effluent is shown and the toxicity effect on the populations of anaerobic bacteria is evaluated. The results of the anaerobic biodegradation assays show that 62% of the wastewater compounds, measured as COD, could be consumed. An upflow anaerobic sludge blanket (UASB) reactor was used in the evaluation, it has a diameter–height ratio of 1:7, and 4-liter volume. The inoculum was obtained from a UASB pilot plant that treats brewery wastewaters. At the beginning of the operation, the biomass showed an anaerobic activity of 0.58 gCOD/(gVSS×d), it decreased only 2.5% in the subsequent 4 months. After 35 days of continuous operation, the reactor was operated at different steady states for 140 days. The COD was maintained at 2200 mg/l in the feed. The results were: organic loading rate (OLR): 4.3 kg COD/(m³×d), hydraulic retention time: 12 h, superficial velocity: 1 m/h, average biogas productivity: 290 L CH₄/kg COD fed, biogas composition: 70–75% methane and a COD removal percentage >75%. ©     

Utilization of a leather industry waste

In the production of leather the main waste that remains after splitting of limed hides before tanning is the lowest layer of the skin together with the underlying fatty tissue (subcutis). It is characterized by a very high water content (up to 870 g kg⁻¹) and a balanced content of protein (40–60 g kg⁻¹ of the dry mass), fat (10–20 g kg⁻¹) of the dry mass) and carbohydrates. The object of this work was to elaborate a method to process this waste into useful products. The treatment proposed involves washing to remove the inorganic salts, separation of fat and extraction of collagen in hot water solution and additional extraction of protein from the insoluble residue after hydrolysis with alkaline proteinase. This results in the isolation of three fractions: fat—cattle tallow (4–12% of the total mass of the initial material), collagen hydrolysate—glue (5–10%) and protein concentrate for fodder (1–3% yield). Up to 95% of the protein in the initial material was extracted. Further purification of the collagen hydrolysate fraction into edible gelatin was achieved. The proposed method is applicable to every leather factory.     

Field scale N2O flux measurements from grassland using eddy covariance

In order to assess nitrous oxide (N₂O) emissions from typical intensively managed grassland in northern Britain fluxes were measured by eddy covariance using tuneable diode laser absorption spectroscopy from June 2002 to June 2003 for a total period of 4000 h. With micrometeorological techniques it is possible to obtain a very detailed picture of the fluxes of N₂O at field scale (10³–10⁴ m²), which are valuable for extrapolation to regional scales. In this paper three of the four fertilizer applications were investigated in detail. N₂O emissions did not always show a clear response. Hourly fluxes were very large immediately after the June 2002 nitrogen fertilizer application, peaking at 2.5 mg N₂O–N m^–2 s^–1. Daily fluxes were averaging about 300 ng N₂O m^–2 s^–1 over the 4 days following fertilizer application. The response of N₂O emissions was less evident after the August fertilization, although 2 days after fertilizer application an hourly maximum flux of 554 ng N₂O–N m^–2 s^–1 was registered. For the rest of August the flux was undetectable. The differences between fertilization events can be explained by different environmental conditions, such as soil temperature and rainfall. A fertiliser-induced N₂O emission was not observed after fertilizer application in March 2003, due to lack of rainfall. The total N₂O flux from June 2002 to June 2003 was 5.5 kg N₂O–N ha^–1y^–1, which is 2.8% of the total annual N fertilizer input.     

Pools and Fluxes of Cations,Anions and Doc in Two Forest Soils Treated With Lime and Ash

The effect of liming and ash treatment on pools, fluxes and concentrations of major solutes was investigated at two forestedsites (Norway spruce) in S. Sweden. One site was treated 15 yrprior to sampling (Hasslöv-Hs; dolomite: 3.45 and 8.75 t ha^-1) and the other 4 yr before (Horröd-Hd; dolomite: 3.25 t ha^-1; wood ash: 4.28 t ha^-1). Effects of limingwere most pronounced in the O horizon solutions where higher pH,elevated Ca (120–700 M) and Mg (50–600 M) were observed as compared to control plots. The impact on the mineralsoil was more moderate. Soil solution concentrations were combined with modelled hydrological flow to calculate mass flows,which largely followed the trends of the solution composition. Liming also resulted in large increases of both exchangeable Caand Mg as well as effective cation exchange capacity (CEC_E;2–5 times the controls). The base saturation (BS%) was raised to 60–100% in the O horizon while in the mineral soil elevated values were only seen at the Hs site (20–60%; down to 10–15 cm depth for 8.75 t ha^-1). Ash treatment did notaffect either the soil solution nor the exchangeable pool to thesame extent as lime. In general, the impact at the Hd site was less pronounced especially in the mineral soil, which might be due to shorter treatment time (4 vs. 15 yr) and also differentthickness of the O horizon. Budget calculations for Ca and Mg originating from the lime showed that a major part of the Ca (40–100%) was retained in the top 30 cm of the soil, of which30–95% was present in the O horizon. The mobility of Mg wasgreater and it was estimated that a significant part had been leached from the profile (30 and 50 cm depth) after 15 yr. Increased mass flows of NO₃ ^- due to nitrification resulting from liming at the Hs site were calculated in the range120–350 mmol m^-2 yr^-1 (or 1.2–3.5 kmol ha^-1 yr^-1). There was significant leaching of Al (25–60 mmol m^-2 yr^-1), of which about 70% was inorganic, in thelower B horizon at both sites with no influence of liming.     

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.