The major aim of this study was to investigate various leaching methods for the recovery of zinc and lead from blended neutral leach residues of &Ccedil / inkur having a composition of 12.59 % Zn, 15.21 % Pb, 6.45 % Fe, 0.054 % Cd. Initially water leaching tests were performed at various conditions of leaching temperature, reaction time and particle size. The optimized conditions for water leaching were found to be 2 h, 95&amp / #61616 / C and 250 g/l pulp density with a final pH of 5.9. However, the zinc recovery value of 10.26 % was not adequate for industrial scale operations itself. In acid leaching trials / acid concentration, temperature, reaction time and particle size were the chosen variables. At the optimized condition of 150 g/l H2SO4, 95&amp / #61616 / C, 2 h at 250 g/l pulp density with a final pregnant solution pH of 4.2, the extraction values were determined as 74.87 % for Zn and 39.59 % for Fe. These recovery values were evaluated as suitable for industrially feasible operations while creating a secondary leach residue of a composition of 4.10 % Zn, 19.17 % Pb, 5.52 % Fe and 85 ppm Cd that would not be suitable for pyrometallurgical lead production. After recovering zinc in considerable amount by hot sulphuric acid leaching, NaCl leaching experiments for the extraction of lead were done on the secondary leach residue by taking temperature, time and pulp density into account. The most promising conditions of brine leaching for lead recovery were found as 300 g/l NaCl, 20&amp / #61616 / C, 15 minutes and 20 g/l pulp density that gave approximately 82 % lead recovery with a final residue of 7.87 % Pb, 6.86 % Zn, 8.79 % Fe.

Groundwater contamination caused by agricultural fertilization is a widely recognized problem. In Hawaii, nitrogen fertilization from pineapple and sugarcane fields has posed a threat to several basal aquifers and has been implicated in coastal algae blooms. The concentration of nitrate-N in the Pearl Harbor basin on the island of Oahu was below 2.3 mg/L in the 1950’s and 1960’s, and has increased to as much as 7.6 mg/L in 1992 to 1994. The objective of this dissertation research is to develop a practical methodology for realistically estimating nitrate leaching from fertilized agricultural lands. Numerous mechanisms have impact on the distribution and migration of nitrate in the soil. Nitrogen fertilizer undergoes many N transformations and interactions with the soil and the plant after applications. In this study, an analysis of soil samples was performed to understand the leaching process of nitrate in the root zone of three different cropped fields in Hawaii. A detailed discussion is given to address various factors which control the nitrate transport process. To judge the sampling plan in relation to spatial variation, the field measurements were evaluated statistically by an uncertainty index, which is represented as the density of samples required for the estimate of sample mean of the nitrate concentration to fall within a defined limit of accuracy. In order to predict the effect of nitrogen fertilization on the groundwater contamination with very limited input data, a simple, analytical, lumped parameter model (LPM), was developed. The model can estimate the average nitrate leaching from the root zone in response to agricultural practices, N transformations and other related processes. The model was tested against the field data and two detailed numerical models, LEACHM-N and CERES-Maize. It provides an alternative way to assess nitrate leaching from the root zone with acceptable accuracy. A listing of the program is provided in Appendix 2. Owing to the complex nature of nitrogen behavior in the unsaturated zone, some degree of uncertainty is involved in the development of modeling approaches. In this study, five major sources of uncertainty were identified. These are: uncertainty due to spatial variation, uncertainty related to the accuracy of the input data, uncertainty due to simplifications in the development of the models, uncertainty due to the modeling parameters, and uncertainty due to the complexity of the unsaturated zone in Hawaii. The impact of these uncertainties on simulation results is evaluated. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1996. / Includes bibliographical references (leaves 202-215). / UHM: Has both book and microform. / Water Resources Research Center, University of Hawaii at Manoa

The kinetics of the dissolution of gold and silver colloids in ammoniacal thiosulfate solutions has been studied using oxygen, copper(II) or oxygenated copper(II) as oxidants at pH 9 - 11 and temperature 22oC to 48oC. The effects of the concentration of the main reagents such as copper(II), ammonia and thiosulfate as well as various background reagents have been investigated. Gold and silver colloids have characteristic absorption peaks at 530 nm and 620 nm respectively. Thus, the extent of gold or silver dissolution in different lixiviant systems was monitored using an ultraviolet-visible spectrophotometer. A comparison of the behaviour of gold colloids and powders has also been made. The beneficial or detrimental effects of silver colloid, and background reagents such as silver nitrate, and sodium salts of nitrate, carbonate, sulfite, sulfate, trithionate, tetrathionate anions have also been investigated. Experimental results show that the relative rates and the extent of gold colloid dissolution at 25ºC in different lixiviant systems in a given time interval are in the order: oxygen-cyanide > copper(II)-ammonia-thiosulfate ≈ oxygen-copper(II)- ammonia-thiosulfate > oxygen ammonia-thiosulfate ≥ oxygen-ammonia > copper(II) ammonia. The analysis of electrode potentials shows that Au(S2O3)23- is the predominant gold(I) species in the lixiviant solutions containing oxygen or copper(II) as oxidant and thiosulfate or mixed ammonia-thiosulfate as ligands. During the reaction of copper(II) with thiosulfate in ammoniacal solution without oxygen, the measured potential using a platinum electrode represent the redox couple Cu(NH3)n2+/Cu(S2O3)m1-2m (n = 4 or 3, m = 3 or 2) depending on the concentrations of thiosulfate and ammonia. The initial dissolution rates of gold colloid by oxygen in copper-free solutions show a reaction order of 0.28 with respect to the concentration of dissolved oxygen, but independent of the concentration of ammonia and thiosulfate. The reaction activation energy of 25 kJ/mol in the temperature range 25°C to 48°C indicated a diffusion controlled reaction. The initial dissolution rates of gold colloid by oxidation with copper(II) in oxygenfree solutions show reaction orders of 0.41, 0.49, 0.60, 0.15 and 0.20 with respect to the concentrations of copper(II), thiosulfate, ammonia, chloride and silver respectively. The presence of silve (I) or chloride ions enhances the rate of gold dissolution, indicating their involvement in the surface reaction, possibly by interfering with or preventing a passivating sulfur rich film on gold surface. An activation energy of 40-50 kJ/mol for the dissolution of gold by oxidation with copper(II) in the temperature range 22°C to 48°C suggests a mixed chemically/diffusion controlled reaction. The dissolution of gold by oxidation with copper(II) in oxygen-free solutions appears to be a result of the reaction between gold, thiosulfate ions and the mixed complex Cu(NH3)p(S2O3)0. The half order reactions support electrochemical mechanisms in some cases. The initial dissolution rates of gold colloid, massive gold and gold-silver alloys by oxygenated copper(II) solutions also suggest a reaction that is first order with respect to copper(II) concentration. High oxygen concentration in solutions has a negative effect on the initial rate of gold dissolution and overall percentage of gold dissolution, indicating that oxygen affects the copper(II), copper(I) or sulfur species which in turn affects the gold dissolution. The surface reaction produces Au(NH3)(S2O3)- and Cu(NH3)p+. The mixed complexes Au(NH3)(S2O3)- and Cu(NH3)p+ re-equilibrate to the more stable complexes Au(S2O3)23- and Cu(S2O3)35- in solution. The dissolution of gold powder by oxidation with copper(II) in oxygen-free solutions shows the same trends as that of gold colloid. The presence of silver(I) or chloride ions enhances the initial rate and percentage dissolution of gold colloid and powder. The dissolution kinetics of gold powder and colloid follow a shrinking sphere kinetic model in solutions of relatively low concentrations of thiosulfate and ammonia, with apparent rate constants being inversely proportional to particle radius. The best system for dissolving gold based on the results of this work is the copper(II)-ammonia-thiosulfate solution in the absence of oxygen or in the presence of oxygen. In the absence of oxygen, copper(II) 1.5-4.5 mM, thiosulfate 20-50 mM, ammonia 120-300 mM and pH 9.3-10 are the best conditions. The presences of carbonate and sulfite have a significant negative effect on the dissolution of gold. The presence of sodium trithionate shows a beneficial effect in the first two hours, while sodium tetrathionate or lead nitrate have a small negative effect and sodium nitrate showed no effect on the dissolution of gold. Silver nitrate and sodium chloride also show beneficial effects. In the presence of oxygen, copper(II) 2.0-3.0 mM, thiosulfate 50 mM, ammonia 240 mM and pH 9.3-9.5 are the best conditions.

Following over 100 years of agriculture and continuous phosphorus (P) fertilizer application in the south west of Western Australia, there is a growing risk of P transport from cropping and pasture land to streams. However, soil and landscape factors affecting the likelihood of P losses and of stream water contamination have not yet been assessed for the South coast region of Western Australia. The present investigation was conducted in the Fitzgerald River catchment located ~ 400 km south east of Perth, to identify risk of P losses from agricultural land to streams, through an understanding of how P is retained within complex landscapes and released via surface and subsurface flow paths. The 104,000 ha catchment is in a moderately dissected landscape (average annual rainfall 450 mm) and discharges into the World Heritage listed Fitzgerald Biosphere. The main use of cleared land in the catchment is broad-scale agriculture, primarily winter grain cropping and pasture for livestock. The aim of an initial study was to identify the areas with high soil P concentrations and their relationship to factors such as soil type, topography, management (e.g. fertilizer and manure inputs, and uptake by crops or forage) and how variations in soil P concentrations were related to soil physico-chemical properties, P fertilizer management and landscape position. A wide variation in P concentrations was observed across the catchment, but few of the samples exceeded Colwell extractable P levels of 30 mg/kg in the 0-10 cm layer which is regarded as a critical level for crop and pasture productivity. The western area of the catchment, which was cleared earlier (before 1966) than the eastern area had a greater prevalence of loam soils, and higher Colwell-extractable P concentrations (average)22 mg/kg vs. 13 mg P/kg) due to soil type effects and higher P accumulation over time. Risk of P loss from the east and west of the catchment is expected to vary due to textural and topographic differences and P history (P fertilizer input and uptake by crops). The CaCl2-extractable P in the catchment was negatively correlated with oxalate extractable Fe (Feox) in soils. This suggests that P may be transported as particulate P (PP) on loam and clay soils due to sorption of P on oxides surfaces, while on sand soil leaching losses may be more likely. On loam and clay soils, higher sodicity and the dispersive nature of subsoils may increase the risk of both dissolved P (DP) and PP loss due to the effects on hydraulic conductivity of the profile. Hedley's fractionation scheme was used to quantify P fractions in the order of decreasing lability, viz: resin-P > NaOH-Pi > NaOH-Po > acid-P (H2SO4-P) > residual-P. Surface soil had higher resin and NaOH-Pi, which are regarded as water-soluble and readily exchangeable P forms, respectively and expected to contribute to DP in the runoff losses. The residual P was the largest fraction followed by the hydroxide extractable organic-P fraction (NaOH-Po): the former was positively correlated (r) with clay content, organic carbon (OC) and pyrophosphate extractable Fe and Al (0.48**, 0.61**, 0.69** and 0.58**, P < 0.01). A relatively higher value of NaOH-Po in the subsurface layer and positive correlation with OC (r = 0.45**, P < 0.01) suggests potential mobility of P as soluble organic P in run-off, throughflow and leachate. Phosphorus sorption and its relationship to soil properties was used to assess the potential P release from the catchment soils. Values of P sorption maxima varied from 1111-3333 mg/kg for surface soils and 1010-2917 mg/kg for subsoils. The P sorption isotherms conformed better to the Freundlich equation than the Langmuir equation. A highly significant negative correlation between CaCl2 extractable P and Feox in surface soils (r = -0.65**, P < 0.01) suggests that P was bound to hydrated Fe oxide surfaces and this may determine the concentration and dynamics of loosely bound P equilibrating with leachates and eroded particulate materials. On the other hand, high surface organic matter and the high proportion of total dissolved P in organically bound form may inhibit P sorption on clays and sesquioxides, which would increase P mobility through leaching or runoff losses. The relationship between soil P concentration and degree of P stratification in the top 0-10 cm of soils along five toposequences was examined to predict the effect on runoff P losses. The total Colwell-P content of the 0-10 cm layer of soils in the catchment was very low in comparison to other studies on P losses from agricultural soils, but soils showed higher P concentration at 0-1 cm depth compared to 5-10 cm (average 37 mg/kg vs. 19 mg/kg). The higher extractable P concentration in the 0-1 cm layer will create a greater P mobilization risk in surface runoff and leachate than analysis of the 0-10 cm layer might suggest. Assessment of P risk using the 0-10 cm data would still be reliable as P concentration in the 0-1 cm layer was linearly related (R2 = 0.59) with concentration in the 0-10 cm layer. The sampling at varied soil depths will result in different critical P levels for estimating the risk of P enrichment in runoff. In a glasshouse study with intact soil columns, initial high P concentrations in leachate decreased with leaching events suggesting that macropore flow dominated in initial leaching events changing later to matrix flow. The hydraulic behavior of clay and loam soil below 10 cm depends largely on structure and the type of clay minerals and exchangeable Na. Higher levels of exchangeable Na in the subsoil might increase dispersion of clay particles resulting in low permeability leading to ponding of surface water or lateral movement of water at the interface of sand A and clay B horizons. Lateral water movements increase the risk of P losses in the form of DP, dissolved organic P (DOP) or PP. The P concentration in all the P forms (DRP, DOP and TDP) increased significantly with P rates of application (P < 0.01). The DRP concentration was < 2 mg/l in unfertilized columns but an increase to 11 mg/l was observed with P application at 40 kg P/ha. The higher proportion of DOP relative to DRP and its correlation with TDP indicates that the DOP was the major form of P in leachate. However, the estimation of DOP which was by subtraction of DRP from TDP generally overestimates OP concentration. The TDP load from unfertilized soil was < 0.20 mg/l in runoff and < 2.40 mg/l in throughflow but increased with P application (20, 40 kg P/ha) for both packed box and field studies. Under field conditions, higher P loss was found with broadcast P application compared to drill placement. The higher load of DOP as a proportion of TDP and its significant relationship with TDP in runoff (R2sand = 0.81; R2clay = 0.79) and throughflow (R2sand = 0.94; R2clay = 0.98) in field and box studies also suggests DOP was the major form of P loss from soil. Dissolved OP concentration increased significantly with increase in soluble organic carbon (SOC) in soil solution at 5 cm depth (P < 0.05). Consequently, the amount of organic matter dissolved in soil solution may influence P sorption and mobility. Relatively higher affinity of soil for sorption of DRP compared to DOP might allow DOP to be more mobile through the profile. Higher PP load in clay soil in throughflow indicates subsurface lateral flow along the interface with the horizon of dispersive clay might be an additional risk factor regarding P mobility in clay soils of the catchment. The runoff, throughflow and leachate were dominated by eroded particles of clay and colloidal organic materials. However, the soil solution collected though 0.1 m pores in the Rhizon samplers had a similar dominance of DOP to the < 0.45 jum filtered samples in runoff and throughflow. This reduces the likelihood that the so-called DOP fraction was mostly P associated with PP in the 0.1 to 0.45 jum size fraction. The composition of DOP in soil solution collected through Rhizon samplers (< 0.1 jum) might provide important insights for P mobility since this more effectively excluded PP than in the < 0.45 jum filtrate used for runoff and throughflow samples. The DOP in soil solution (< 0.1 jum) might be associated with fine colloidal compound such as silicates, metallic hydroxides, humic acids, polysaccharides, fulvic acids and proteins. If so, then most, but not all of the DOP fraction would be organically bound. However, this requires verification. In conclusion, soil P levels across the catchment were never very high when assessed in the 0-10 cm layer, but levels in the 0-1 cm layer were more than twice as high. Overall, < 1 % of land area of the upper Fitzgerald River catchment had Colwell-P levels > 30 mg/kg (0-10 cm) and hydrological connection to streams. In addition, another 7 % of land had Colwell-P levels > 15 mg/kg, which appears to be a change point in soils for the release of CaCl2 extractable P. These areas, which are predicted to represent critical source areas of the catchment, need careful management. The high proportions of TDP as DOP in runoff, throughflow and soil solution suggest DOP was the major form of P loss from soil. Phosphorus losses from the catchments are also likely in the form of PP in clay and loam soil but leaching losses are more likely in sand. High exchangeable Na in the subsoil of loam and clay soils increases dispersion of clay particles resulting in low permeability of subsoil and greater lateral P mobility as throughflow at the interface of sand and clay textured horizons. In general, soils of Fitzgerald River catchment had low soil P, but nevertheless significant risk of P loss at Colwell-P > 15 mg/kg. This study provides baseline information for P loss risks in the wheatbelt of WA. Stream water quality monitoring instruments were installed in the upper Fitzgerald River Catchment at 5 stream locations by CSIRO to measure base line concentrations of P. The measured P concentrations were higher than ANZECC trigger values (> 0.05 mg P/l) for management response over the three-year monitoring period (2005-07). Hence this and many other catchments on the south coast and wheatbelt of south west Western Australia need assessment for P loss risks. Previous emphasis in south west Western Australia on P losses from sandy coastal soils under pasture may need to be reconsidered. In the South coast region, cropping land in the medium rainfall zone may still represent a risk of P loss to waterways and risk to water quality. The present study evaluated the risk of P loss based on soil P forms and their mobility. It suggests greater attention needs to be given to the difference between clay and loam soils with dispersive or non-dispersive sub-soils, and to the composition and mobility of DOP. However, a more complete understanding of P loss risks depends on follow-up studies on hydrological flow and connectivity in the upper Fitzgerald River catchment and similar landscapes of south west Western Australia.

Diss. (sammanfattning). Uppsala : Sveriges lantbruksuniv., 2003. / Härtill 3 uppsatser.

Diss. (sammanfattning). Umeå : Sveriges lantbruksuniv., 2003. / Härtill 5 uppsatser.

Diss. (sammanfattning) Stockholm : Tekn. högsk. / Härtill 4 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2004. / Härtill 4 uppsatser.

Diss. (sammanfattning). Uppsala : Sveriges lantbruksuniv. / Härtill 4 uppsatser.

Thesis (PhD) -- University of Western Sdyney, 2001. / "A thesis presented in accordance with the regulations governing the award of the degree of Doctor of Philosophy, University of Western Sydney" "November 2001" Bibliography: leaves 249 - 254.