Search Documents

By Gülay Bulut, Ünzile Yenial

"Water composition has a significant effect on flotation. A better understand the role of water composition in flotation is very important for process quality and performance. Based on source of process water, the concentrations of the dissolved ions, hardness, contaminants and residual composition of reagents can varied in the process water. The various water resources employed during lead and zinc flotation caused activation, depression or selectivity effects on minerals due to the presence of different ions in solution. Metal ions in these water resources were adsorbed on the ore, whilst ions associated with gangue minerals were released into the flotation pulp.This paper includes a research for the effect of different water compositions on lead and zinc sulphide flotation. Experiments were carried out five types of water such as tap water, recycling water, tailing dam water, underground mine water and sea water. The ore sample was obtained from Esan Balikesir-Balya mine. The mineralogical study of ore sample shows that it contains mainly galena, sphalerite, pyrite, hematite, quartz, diopside, epidote, calcite, and chlorite. It is found that recycling water and tailing dam water has a positive effect on recovery of lead and zinc minerals and detrimental effect on content of both minerals. This result may explain with remaining reagents in these waters. Underground mine water and tap water gave nearly the same recoveries of zinc. Sea water affects the recovery lead and zinc negatively."

Jan 1, 2014

By Achilles Dutra, Everton Santos, José Oliveira

The beneficiation of phosphate ores by froth flotation is the most efficient process used to separate apatite from gangue minerals like calcite, dolomite and quartz. However, the similarity of surface properties between apatite and calcite generally lead to non-selective adsorption of reagents, rendering the selective separation of these minerals a worldwide problem. The phosphate deposit of Itataia, State of Ceará, Brazil, studied in the present work, presents a complex mineralogical composition having uranium associated with the apatite mineral. The main gangue minerals are calcite and quartz. The bulk flotation of apatite and calcite with anionic collectors in an alkaline medium followed by the selective flotation of calcite at pH 5.5 using phosphoric acid as well as citric acid as depressant have been suggested for this ore. This paper presents the results of contact angle measurements obtained using jojoba oil, a natural reagent composed mainly of gadoleic acid (C20:1) and long-chain fatty alcohols (eicosenol and docosenol), as an alternative collector for the selective separation of apatite and calcite minerals. The hydrophobicity studies were carried out using a computer controlled contact angle goniometer. Additionally, the collector adsorption was evaluated via electrophoretic mobility and FTIR measurements. The results indicated that a high selectivity can be obtained by using jojoba oil as collector in a slightly acid pH range, without the use of depressant. The best results were achieved with a jojoba oil concentration of 200 mg.L-1 at pH 6.5, where the apatite was fully hydrophilic and calcite showed a high hydrophobicity (? > 60 º).

Jan 1, 2014

By J. Kwon, D. Lee, H. Cho

"The use of the combined grinding and liberation model to predict liberation characteristics of iron ore comminuted by a ball mill was studied. Comminution characteristics were obtained using the one-size fraction method. The iron ore samples were crushed and separated into a number of narrow size fractions by screening. The size fractions were further divided by magnetic separation into three classes: concentrate, middling, and tailings. Subsequently, various size-grade classes were subjected to ball milling, and the results were analyzed in terms of the kinetic grinding model. The mineralogical textures of the grinding products were analyzed using mineral liberation analysis. The distribution of iron content within the size fractions was characterized by the beta distribution combined with the Andrew–Mica diagram. It was found that the grinding characteristics of the iron ore samples varied slightly with the iron content. However, the liberation characteristics were well described by the same set of liberation model parameters, regardless of composition. The variation in grinding kinetics with composition and the liberation model parameters was used in the combined comminution–liberation model to predict the evolution of the size-composition matrix as grinding proceeded. The predicted results agreed well with the experimental results. The developed model can be used to construct the yield–recovery graph and to calculate the liberation efficiency to determine the size reduction threshold for efficient separation. INTRODUCTION In mineral processing, comminution is usually the first step that ores undergo to liberate valuable minerals from gangue minerals. Generally, as the particle size decreases, higher liberation can be achieved. However, excessively small particles are unfavorable to subsequent processes, such as separation. Moreover, comminution is a highly energy-consuming process itself that accounts for approximately 60% of all energy used for processing. Therefore, there is a definite need to increase energy efficiency by applying adequate stress so that a high degree of liberation can be acquired at the coarsest size without overgrinding. To this end, it is essential to develop a model to predict the liberation of minerals as a function of size reduction."

Jan 1, 2018

By P. Knüpfer, B. Babel, M. Rudolph, F. Perez Maldonado, U. A. Peuker, L. Ditscherlein

"In heterocoagulation processes for the separation of mineral particles, the most famous being froth flotation, the main characteristic of separation is a differing wettability of the constituents to be separated. This most crucial property in the economically important process of flotation is often only and incompletely, quantitatively described in terms of contact angles against water. A water contact angle larger than 90° is referred to as hydrophobic and hydrophilic vice versa. Looking at Young’s equation shows that it is actually the surface energy of the solid in interaction with the surrounding phases and their surface energies (or surface tensions for liquids) which describes whether there will be hydrophobic/hydrophilic hydration interactions leading to attraction or repulsion. This, we have previously published for various more or less hydrophobic minerals in correlation to their flotation response, i.e. flotability (c.f. Rudolph & Hartmann, Coll.Surf.A 513, 380-388). In the same paper we also discussed the heterogeneity of wettabilities as assessed with the novel method of inverse gas chromatography. Furthermore we have also reported on hydrophobic force distributions as assessed with atomic force microscopy which are as well due to wettability heterogeneities (c.f. Fritzsche et al., Coll.Surf.A 459, 166-171).In this paper we present wettability distributions of different substrates and particles with various surface roughnesses/shapes and degrees of hydrophobization as assessed with iGC, AFM and dynamic sessile drop analyses. We are putting the results in context in unifying models and present methodologies helpful to make use of the fundamental information and their impact on the actual industrial separation process in fundamental process models. Besides froth flotation we also emphasize the impact on selective hydrophobic flocculation process."

Jan 1, 2018

By Dilip. Makhija, Asim. K. Mukherjee, Tamal Ghosh, Abhay Patra

In India around 15-20% of Run of Mine (ROM) from any iron ore deposit reports to slime dams as byproduct of iron ore beneficiation process. The proportion of iron ore slime to ROM will increase in future with higher proportion of lean grade ores in ROM. Furthermore, tonnages of iron ore slime will also increase with increasing demand of iron concentrate. Presently, this slime is stored in the dam in the absence of beneficiation technology. A beneficiation flowsheet has been developed at Tata Steel. This process produced concentrate of 2.2% alumina with 40 % yield from slime of 7-9% alumina. The iron content in the reject will be less than 40% thus adhering to the regulatory norm. Pilot scale study show waste from slime beneficiation is a good raw material for making a variety of building materials. Waste from slime beneficiation also has soil amendment properties. Pilot scale studies show productivity of rice increased when the waste of slime beneficiation process is mixed with soil. On commercialization of this zero waste technology slime generated from the iron ore washing plant will be completely used. In this paper the result of the pilot scale studies on slime beneficiation and utilization processes towards soil making and making of building materials are discussed in detail.

Jan 1, 2014

By Stephen Gay, Dewetia Latti

"When improving a plant a mineral processing engineer would like to know the mineral composition distribution. In order to assess this distribution in particles, as compared to the corresponding distribution in particle sections, a procedure needs to be applied to the observed particle sections. Such a procedure is called a stereological correction. There exists many stereological correction procedures, but one group of such procedures is based on using those stereological equations that do not require making assumptions regarding particle shape or texture.In particular Davy derived an equation to estimate the covariance of mineral composition distributions for particles from both particle sections and linear intercepts. Furthermore, this covariance can also be used to measure the variance of the composition distribution of each mineral.This paper shall present results verifying this equation. The experimental method was based on obtaining particle information from serially-sectioned particles. Particle samples selected for serial sectioning displayed a range of natural textures including liberated, binary and composite particles. The exposed surface of the polished sections were analysed using QEM*SEM. This procedure was repeated until all of the grains have been polished away. The covariance of mineral distributions were calculated from the serial sections and compared with that calculated using Davy’s equation."

Jan 1, 2003

By Aysan Molaei, Kristian Waters

Solvent extraction is the one of the most common techniques for recovering metal ions from aqueous systems. However, solvent extraction is generally limited to relatively high concentrations and requires a high organic/aqueous ratio. Predispersed solvent extraction (PDSE) is a modified solvent extraction technique in which organic phase pre-comminute into colloidal liquid aphrons (CLAs). In this study, the extraction of copper by the PDSE technique was investigated. The main focus of this study was on the characterization and application of CLAs under different operational conditions, and to investigate the effects of different parameters on the extraction of copper from dilute streams. The effect of phase volume ratio (PVR), initial extractant concentration and initial copper concentration was studied and optimum conditions for copper removal using CLAs generated by LIX 984N as extractant, oil soluble and water soluble surfactants were proposed. Experimental observations indicated that PVR and initial LIX 984N concentrations had a significant effect on copper extraction.

Jan 1, 2014

By Y. Q. He

The methodology of active pulsing air separation is a new method for dry material classification. Especially, it is suitable to electronic scraps disposal and re-utilization. By studying the difference of drag coefficients of the particles moving through areas of varying Reynolds numbers, and considering the extra-mass forces acting on the particles in the active pulsing air field, models of the dynamic motion which particles follow were developed. A computer simulation was prepared that showed the traces of particles with different densities and/or diameters, but similar aerodynamic characteristics, as they moved through the turbulent flow, to modify and define the parameters of the models. The simulation was found to predict the observed results with artificial tracing spheres being separated by the laboratory equipment. The separation performance, as being affected by the particles, nature, the air velocity, the pulsing frequency and the air pattern, is discussed. In general, lower density particles are more responsive to variations in airflow velocity. In addition, an industrial scale active pulsing air separator was designed, and it provides a new and efficient method for resource re-utilization in China.

Jan 1, 2014

By J. Gebhardt, D. McBride, M. Cross, S. Gilbert

Heap leaching of ores containing chalcopyrite offers a low cost option to treat low grade complex copper sulfide ore bodies. However, the slow leach kinetics of chalcopyrite at ambient conditions typically results in unacceptably low recoveries. As the mineralogy of new ore deposits becomes more complex and the effects of gangue chemistry exert a greater influence on copper sulfide leach behavior, the control of leach reaction chemistry becomes more critical. Computational fluid dynamics (CFD) technology has been useful in the capture of multi-phase interactions and provides a path to simulate complex fluid flow, gas and liquid phases, through the heap, along with species transport. Coupling the flow models with the reactive mineral dissolution, and the sometimes competing aqueous chemical and solid-liquid reactions, yields a comprehensive model of the heap leach process. The leach kinetics of chalcopyrite dissolution in heap conditions is examined, and the incorporation of chalcopyrite leach kinetics in the CFD model is described. The application of the model to investigate optimization of the heap is discussed.

Jan 1, 2014

By K. Sasaki, H. Miki, Y. Muta, T. Hirajima, G. P. W. Suyantara

"Selective flotation of chalcopyrite and molybdenite is continuing problem since its selectivity is not perfect and current NaHS process needs closed system flotation plant because of hydrogen sulfide emission on acidic condition. Some alternative additives investigated as chalcopyrite became hydrophilic and molybdenite kept hydrophobic. XPS analysis indicated chalcopyrite became hydrophilic since iron and copper sulphate, hydroxide was covered on the surface whereas molybdenite kept hydrophobic since only molybdenite can be seen. Flotation experiments of chalcopyrite and molybdenite mixture sample indicated excellent separation that 95% of molybdenite can be recovered as froth and 93% of chalcopyrite can be recovered as sink. Flotation experiments with real bulk flotation concentration indicated similar separation result compared with current NaHS additive system. Possible mechanisms and detailed phenomenon were investigated based on the surface analysis and thermodynamic calculation etc. this alternative additive is easy to handle compared with NaHS since it does not emit effluent gas and commercially preferable.INTRODUCTIONMany copper mine often associates molybdenite (MoS2) as trace mineral. It is important to separate molybdenite and copper mineral efficiently since molybdenite is valuable mineral and also contamination of molybdenite into copper concentrate decrease concentrate value. Conventional separation of copper sulfide and molybdenite has been achieved with sulfide bulk flotation followed by selective molybdenite flotation with NaHS addition since NaHS works as a depressant for copper sulfide (Bulatovic, 2010; Ansari and Pawlik, 2007b). However, this current process shows imperfect molybdenite recovery (Liu et al., 2012, Zanin et al., 2009) and depressant such as NaHS needs to be used under specific flotation plant since it might be environmental contaminant (Ansari and Pawlik, 2007a). there are still unknown on the effect of depressant NaHS, but one of the theory is NaHS reductant effect. It is worth to investigate the effect of other reductant as depressant on chalcopyrite. On this research, typical reductant, Na2SO3 are added to utilize for selective flotation of chalcopyrite and molybdenite."

Jan 1, 2018

By F. Bello, R. Yanez, M. Pinto, T. Errazuriz

"Throughout its operation, Minera Esperanza (ME) will deposit one of the largest tonnages rates of high density tailings in the world with a solids concentration of close to 67% by weight. The tailings presently being deposited have a solids concentration of approximately 62% - 64%, and so cannot be used to directly characterize the flow and deposition characteristics of the higher concentration tailings. To increase the knowledge of the behaviour of their tailings, ME, with the support of Golder Associates, developed a large scale tailings deposition test with a capacity of 30,000 tonnes per day (1,200 m3/h). The test was carried out by depositing tailings into two large cells or paddocks in five stages. Multiple spigots were used to allow different flows to be deposited. At each stage, topographical surveys of the natural terrain and the geometry of the deposited tailings, as well as continuous flow measurement and periodical rheological characterization of the discharged tailings were conducted to create a data set against which beach slope models could be calibrated and then used to predict performance of the higher concentration tailings under different deposition scenarios. This study adopted the beach slope prediction model proposed by A.L. Li (Li, 2011). The model was successfully adjusted to the observations made during this large scale field test by applying the values measured in-situ. This paper presents the application of the model, the results obtained, the findings, and the analysis of possible future scenarios. The model was applied, using the discharge flow rate, the geometrical characteristics of the discharge area, and the rheology with its variation along the beach to estimate the development of the beach formation and the steady state of the beach slopes. Through the use of dimensionless variables, the model was applied to higher solids concentration scenarios, obtaining results that would allow beach slope estimation at different deposition stages in multiple scenarios of varying parameters such as flow, rheology and geometry of discharge area."

Jan 1, 2014

By Fu Ping-Hao, Sergio Mauricio Vianna, Ewen Silvester, Emmy V. Manlapig

"Over the last 5 years, an ambitious project has been undertaken at the Julius Kruttschnitt Mineral Research Centre (JKMRC) aiming to isolate, study and, if possible, model the effect of particle size, liberation and collector adsorption density on the floatability of mineral particles. As part of this project, we have conducted highly controlled flotation test-work, combined with state-of-the-art solution and surface analytical techniques such as High Performance Liquid Chromatography (HPLC), Time of Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) and detailed mineralogical analysis to fully characterize the flotation behavior of a natural ore.The flotation tests were undertaken using a high-grade lead-zinc ore from BHP-Billiton’s Cannington mine (Australia) in a specially designed continuously operated laboratory scale flotation rig. Solution and adsorbed collector concentrations were measured independently during the course of the flotation tests using HPLC based ex-situ techniques. Liberation studies were performed using the JKMRC Mineral Liberation Analyser (MLA) on selected size intervals of different streams to estimate the specific surface area of galena. These results were used to calculate the collector adsorption density (collector coverage) on galena particles, with the eventual aim of developing a mathematical model describing the relationship between pulp chemistry, feed mineralogy, and floatability of galena particles."

Jan 1, 2003

By Wolfgang Öfner

Many technical processes also yield dusty residues which usually contain appreciable amounts of valuable matter. Often they also accumulate substances detrimental to the process. Dumping them entirely in landfills wastes raw material and causes high disposal costs, but recycling them without prior treatment is often not feasible. Physical separation processes are preferable because of their rather low energy demand. In order to develop such treatment systematically, the residues must be characterized properly. The technique for such a characterization is taken from mineral processing: perfect fractionation according to continuous properties of the particles supplemented with chemical analysis are used for plotting the Henry-Reinhardt chart. This represents the benchmark for assessing actual separation processes and tests. Their results are compared in terms of ?selectivity? and plotted in the kappa chart. In this paper, Henry-Reinhardt chart and kappa chart are applied to several different types of residues from iron and steel production and show their potential for being upgraded before reutilization in the production process. This approach is suitable for virtually all dusty residues from other industrial processes as well. Keywords: residue, dust,iron and steel, process development, Henry-Reinhardt chart, kappa chart

Sep 1, 2012

By Thomas Mütze, Anja Hirte, Ursx Peuker, Thomas Kuhn

"The comminution behavior of two ferromanganese nodules samples of the equatorial northeast Pacific has been examined as a basis for the separation of two kinds of metal-rich layers. Those layers were finely grown together during nodule formation and are one reason that the exploration of deep-sea minerals calls for the development of new mineral processing concepts. Therefore fundamental analyses of the fracture behavior have been made under compressive and impact stress. Further experiments took focus on the crushing behavior in a jaw crusher and a small scale impact crusher as well as the milling behavior in a dry vibrating mill, a wet planetary ball mill, and a wet agitated ball mill. The comminuted products were characterized by PSD, particle shape, particle density, and porosity. The experiments show a low stress resistance of the ferromanganese nodules. Compared to compressive stress, impact stress turned out to be the more effective for crushing. Both samples showed no significant difference in the comminution behaviour which makes differing mechanical treatments unnecessary. In both cases particle sizes below 1 µm were achieved by wet grinding. This particle size is necessary to separate the two kinds of metal-rich layers which is part of continuative studies."

Jan 1, 2014

By John Ralston, Stephen Grano, Yongjun Peng, Daniel Fornasiero

"A specially designed mill which allowed the control of pH throughout grinding was used to study the effect of grinding conditions on galena flotation and galena separation from pyrite. The changes occurring on the mineral surface during grinding were investigated by EDTA extraction and ToF-SIMS measurements.Galena flotation and galena separation from pyrite were strongly dependent on the type and amount of oxidation species produced on galena and pyrite surfaces under different grinding conditions. Iron oxidation species depressed both galena and pyrite flotation, whilst lead oxidation species activated pyrite flotation but had little effect on galena flotation. Optimum galena flotation and galena selectivity against pyrite were achieved by selecting grinding conditions that enabled lead and iron oxidation production to be controlled.Grinding conditions had a large effect on the flotation of the galena particles of different sizes. Flotation of fine galena particles (-10 µm) was depressed by iron oxidation species derived from the grinding media. Chromium grinding medium decreased the production of iron oxidation species and therefore increased the flotation of fine galena particles."

Jan 1, 2003

By J. Yianatos, C. Matamoros, F. Díaz

The non-selective entrainment of fine solids in flotation equipment has a detrimental effect on the concentrate grade. Reduction of solids entrainment (upgrading) is typically related with a loss in recovery of valuable minerals. For improving the froth transport characteristics and flotation cells design, a better understanding and quantification of the actual solids drainage and entrainment processes are required. In this work, the study of solids transport in the froth of a two-dimensional flotation cell was performed. The prototype cell represents a radial section of an industrial flotation cell (130m3) and was operated at steady state. Experimental tests consisted of adding a small amount of radioactive solid tracer (0.3g) near the top-of-froth or near the bottom of froth (close to the interface). The solid was selected as a non-floatable mineral (gangue) in order to evaluate both the solid entrainment into the concentrate as well as the solid drainage into the collection zone. Solid tracer consisted of fine or coarse gangue particles, P80 of 35 and 120 µm, respectively. Twelve collimated sensors located along the froth and collection zones allowed the evaluation of the solid transport in the froth, and the solid drainage from the froth to the collection zone, after tracer addition at different distances from the discharge lip. Results showed that longer distances to the froth discharge lip, as well as higher particle sizes, promotes higher solid drainage from the froth to the pulp zone, while decreasing the solids entrainment into the concentrate. The same result was observed for the solid located near the top-of-froth as well as near the bottom of froth. This information was complemented by the froth surface velocity measurements, using the Visiofroth system, showing a good agreement between the froth bubbles velocity and the solid transport velocity, measured near the discharge lip.

Jan 1, 2018

By A. Otsuki

This paper describes the evaluation method of dispersion and coagulation of silica nano-particles by means of interactive force apparatus. The apparatus measures the size of fine particles in aqueous solution or organic solvent of high concentration and/or low optical transparency. Other conventional apparatus for size measurements (such as, apparatus utilizing dynamic light scattering) are difficult to measure the size of particles in such conditions accurately, due to multi-scattering of light in the sample solution or solvent. The apparatus measures the interactive force between two surfaces, i.e. the gold-coated glass hemisphere and the brass flat plate, (which is fixed at the bottom of the sample cell). The apparatus has three parts, i.e. main part (which consists of electric balance, hemisphere and flat plate), control part (i.e. personal computer, piezo-stage controller and voltage supplier), and detecting part (i.e. multi-meter and oscilloscope). During the measurement, electric field is applied between the hemisphere and flat plate, and thus dielectric particles are arranged toward the direction of electric field in the area between two plates. When the two plates are close to each other, two different forces (i.e. repulsive force and attractive force) will alternately act on particles due to the structure change of the particles. The repulsive force occurs when the structure of particles is stretched by compressive force; whereas the attractive force occurs when the aggregate structure is broken. The cycle of the repulsive and attractive forces is a primary size of particle or size of aggregate, which depends on the degree of agglomeration. The measured size of particles, which is varied depending on their degree of dispersion and coagulation, determined the characteristics of the silica particles. In this research work, the effect of size and concentration of particles in aqueous solution on the degree of dispersion and coagulation of the silica particles were investigated. Spherical silica particles were selected for this investigation due to their variety of size. This apparatus can be used to evaluate the degree of dispersion and coagulation of other nano-particles in various solvents in many process industries.

Jan 1, 2014

By Henrique Kahn, Daniel Uliana, Carina Ulsen, Guilherme Nery

"Gold has been a material in high demand since the dawn of humanity. After hundreds of years of exploitation, the increasingly search for gold occurs in lower grade deposits with greater extraction difficulty. Therefore, for maximum efficiency, deep knowledge of the characteristics of these minerals and their associations is crucial, which is acquired through an accurate and rigorous routine of process mineralogy and batch extraction tests. The industrial gold process extraction occurs by gravity concentration, sulphides flotation and cyanidation. For gravity concentration, it is fundamental to establish the proportion of free or coarse gold grains and its association to heavy minerals; regarding flotation, the most relevant data are the proportion of gold associated to sulphides and their liberation by the surface area; for cyanidation, it is crucial to evaluate gold accessibility and the kinetics of leaching. Thus, the characterization of gold associations and liberation is vital to establish the plant design, to optimize operating plants and to reduce gold losses. Our aim is the characterization of gold occurrence in low-grade Brazilian deposits with complex mineralogical assemblages to support processing flowchart definition and to predict metallurgical recoveries. Gold distribution in light and heavy minerals was evaluated by heavy liquid separation and the occurrence of gold in free or locked particles was carried out on heavy products by SEM-based automated image analysis using the MLA system. All the products of heavy liquid separation were cyanidated in head samples with different milling conditions to evaluate the reaction kinetics and maximum recovery."

Jan 1, 2014

By P. Somasundaran, G. Anastassakis, Z. Pan, D. R. Nagaraj

Gums are often used as depressants for talceous gangue minerals in the flotation of nickel and platinum bearing ores. However, the mechanisms of gum adsorption on talc are not clearly established. In this work, adsorption of guar gum at the talc-solution interface is investigated using spectroscopic and allied techniques. Guar gum adsorption on talc is not affected significantly by changes in solution conditions such as pH and ionic strength. Electrokinetic studies showed that guar gum decreased the negative zeta potential of talc but did not reverse the charge. Fluorescence spectroscopy studies conducted to investigate the role of hydrophobic bonding using pyrene and dansyl probes showed no evidence of the formation of hydrophobic domains at talc-aqueous interface. Urea, a hydrogen bond breaker, reduced the adsorption of guar on talc to the same extent as that for guar/alumina system, in which hydrogen bond plays an important role. All of the above results suggest that one of the main driving forces for guar adsorption on talc is hydrogen bonding rather than electrostatic or hydrophobic force.

Jan 1, 2003

By M. H. Moys, M. M. Bwalya

The use of the Discrete Element Method (DEM) to simulate the interaction of particles in dynamic environments is growing rapidly. This technique is also being applied in the study of milling extensively. However, to date more focus has been on the validation of the model. In spite of the advantages of the detailed information that is available from the simulator, appropriate application of this information remains a daunting task. In this paper a technique that combines particle breakage probability data with the energy spectra generated from the DEM is discussed.

Jan 1, 2003