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By D. Kidd, T. Tucker, L. M. Indergard, S. Davis

"INTRODUCTION The Lisbon Valley Mining Co LLC (LVMC) operates the Lisbon Valley Mine located in SE Utah. The mine includes 3 open pits, 150-acre heap leach pad, and solvent extraction electro winning plant (SX/EW). Approximately 25MM tons of ore has been mined since 2005. The ore is stacked on the leach pad to an average height of 55 feet and occurs as a blend of crushed material (minus 2”) and run-of-mine (minus 24”). The host rocks include Dakota and Burro Canyon Sandstones. Copper occurs finely disseminated in this material at an average grade of 0.46%. Minerology is 63% sulfide, 27% oxide, and 10% insoluble. Total inventory mined through 2016 is approximately 230 MM lbs. METALLURGICAL CONSTRAINTS Copper production is constrained by areas of low permeability ore and geochemical issues, including acid consumption. The intrinsic permeability the ore ranges from 10-2 to 1 Darcy. This permeability does not permit sufficient aeration by natural convection, therefore oxygen transport is largely limited to the mass of oxygen that can remain dissolved in leachates. As a result, greater than 50MM lbs of copper remains in inventory and occurs secondary sulfides, including chalcocite, covellite, and bornite. BIOLEACHING FUNDAMENTALS Due to the higher activation energies of secondary sulfides, notably covellite and bornite, a strong oxidant is needed to remove an electron from the metal-sulfide lattice and release the copper cation into the sulfate solution. This process occurs most efficiently using the strong oxidant ferric iron (Fe3+). Ferrous iron can be oxidized to ferric iron by oxygen via chemical oxidation or biologically; which was measured to occur 500,000 times faster when using microbes versus oxygen.1 The microbes that oxidize ferrous iron (Fe2+) to ferric iron are naturally abundant and will develop biomass when appropriate conditions and nutrients present themselves. Most nutrients are provided by the ore/irrigation (P,N,Mg, Ca & Fe2+) while the others (O2 and CO2) are provided by air. In most cases, oxygen transfer is the rate limiting step during copper sulfide leaching. 1 Lacey & Lawson 1970 FORCED AERATION SYSTEM DESIGN This paper describes LVMC’s efforts to bioleach the remaining inventory by forced aeration. Two basic aeration systems were installed and tested including vertical wells and horizontal piping. Vertical System The vertical system was installed using the mine’s blast hole drilling rig. Wells were constructed using 4” high-density polyethylene (HDPE) connected to 4” polyvinyl chloride (PVC) screens similar to conventional bioventing wells. Ore samples were collected at each well location to characterize the spatial distribution of the remaining inventory along with fines (minus 200 sieve), pH (acid consumption), and iron. A block model of each analyte was developed and mapped in 3D."

Jan 1, 2017

By M. Kalin

"Ecological Engineering and Biological Polishing technology is a decommissioning approach for inactive coal, uranium and base metal operations. To improve acid mine drainage water some fundamental aspects of wetland ecology and sediment microbiology are combined, to provide conditions to allow for biomineralization of the contaminants.This paper summarizes the first records of microbial alkalinity generation in acid mine drainage through the utilisation of the ARUM process. The process requires that the seepage is at pH 4.5 where sulphate reducers utilize sulphate to produce hydrogen sulphide, which in turn precipitates with metals. The pH increase is brought about by alkalinity generating microbes.The ARUM process has been successful in increasing the pH from 2.5 to 7.0. Flow through reactors operated in the laboratory continuously for more than 60 days have removed Ni from 13 mg/L to < 0.01 mg/L. Design parameters are being developed for low flow rates of 5 L/min in a test system receiving seepage from a tailings.1.0 INTRODUCTIONAcid mine drainage associated with mining wastes poses a significant environmental problem. Conventional means to treat acid mine drainage (AMD) use chemical treatment system. Ecological Engineering technology uses natural biological means to curtail and ameliorate AMD during mine operations and at the time of decommissioning. The premise underlying Ecological Engineering technology is that AMD is the result of a natural process enhanced by mining activities. Therefore, in nature, a process providing a natural balance to AMD has to exist, which, when assisted through appropriate means, can counteract the detrimental effects of AMD on the environment. This process is microbial alkalinity generation which is known to occur in wetlands, lake and ocean sediments (Baas Becling et al, 1960)."

Jan 1, 1991

By D. L. Lampshire

Biological leaching using native heterotrophic bacteria was studied by the U.S. Bureau of Mines as a means of extracting manganese from a domestic low-grade wad ore. Column heap leaching simulation techniques were employed using molasses as the nutrient source for the bacteria. These column studies were designed to investigate the effects of molasses medium flow rate, concentration, and replacement interval on the extent and rate of manganese extraction. .Results showed that flow rates between 0.41 and 8.1 L/min/m2 had little impact on manganese extraction. The total amount of molasses used did have a direct effect on the extent and rate of manganese extraction. Manganese extractions over 90-pct were obtained in 12 weeks of bioleaching with 2-week medium replacement cycles.

Jan 1, 1993

By D. J. Adams

Cyanide heap leaching is the predominant technology used in processing low-grade gold ores. During closure ora heap leach operation, residual cyanide must be removed from the process and waste solutions, as well as the heap. Biological cyanide oxidation is a proven, economical technology for destroying cyanide in process and waste waters and spent heaps; The use of biological cyanide degradation eliminates the need for toxic or corrosive chemical oxidizers and has- been implemented at full scale at treatment costs usually <$0.50/1,000 gal. The Applied Biosciences biological cyanide destruction (BCND?) process has been demonstrated to effectively treat cyanide, concentrations up to 350 mg/L. Treated process solutions and wastewaters also contained other contaminants such as arsenic, copper, iron, silver. selenium, mercury, nitrate and zinc, much of which was removed in the cyanide degradation process. Under optimal conditions, microorganisms can rapidly oxidize free cyanide in some process solutions from over 250 mg/L down to 0.1 mg/L in 4 to 5 hr. Cyanide is degraded to ammonia and carbon dioxide, with 50%ofthe cyanide carbon liberated as C02. In general, carbon tank based bioreactors degrade cyanide at significantly higher rates than process or wastewater pond configured treatments, which usually degrade cyanide-more rapidly than in heap treatments. Investigation of cell-free enzyme preparations as an alternative to live microbial cyanide degradation shows promise. Advantages of enzymes over live microbes for cyanide degradation include: (I) the ability to tolerate and degrade higher cyanide concentrations (> I ;000 mg/L), (2) nutrients to support live microbial cells are not required, (3) the effects of other toxic contaminants, such as metals, found in mining waters-are eliminated and (4) the potential for greatly increased kinetics.

Jan 1, 1998

By Robert H. Poppe

The Regional Copper-Nickel Study examined the potential impacts of copper-nickel sulfide mining, concentrating and smelting operations in northeastern Minnesota and gathered extensive monitoring data on the ecological characteristics of the region&apos;s aquatic and terrestrial biota. Because of the many development options possible, the diversity of the region&apos;s ecology, and the uncertainty of future environmental regulatory requirements, the Study did not attempt to measure the magnitude of environmental impacts on specific biological communities from a specific development proposal. The Study provides a broad base of environmental resource and impact information that hopefully will assist mining developers and environmental regulators when assessing specific proposals in the future. The following discussion is not a description of what will happen if copper-nickel development occurs in northeastern Minnesota but an exploration of why certain potential aspects of such development should be carefully considered and adequately understood before unnecessary or irreversible decisions are made.

Jan 1, 1980

By J. Huisman

With the introduction of ever-stricter environmental operating guidelines, capital expenditure restrictions and operational budget cutbacks, the biological method of SO2 removal becomes more and more attractive. Biological treatment of dilute flue gases is a more cost effective technology in comparison to conventional sodium hydroxide scrubbing. Although the investment costs for sodium hydroxide scrubbing is lower, the operational costs are significantly higher. In addition, the end product of the biological installation is sulfur instead of sodium sulfate; and no further wastewater treatment of the bleed from the biological installation is required since heavy metals are removed simultaneously. Another option for the treatment of SO2 containing gas at a sulfuric acid plant is the production of extra sulfuric acid of the discharged SO2 by applying an additional converter. Comparing biological treatment with this option shows much lower investment costs for the biological installation. Sulfur is produced which can be converted to sulfuric acid, so the bio-route will be more cost-effective than an additional converter. In principle, the biotechnological gas cleaning system is an integration of an absorber with a wastewater treatment facility. In the absorber, the SO2 containing gas is brought into contact with the washing water. The effluent absorber liquid contains a mixture of sulfite and sulfate that is converted into elemental sulfur. This conversion takes place in an integrated system; first, the sulfite/sulfate mixture is converted anaerobically into sulfide; secondly, the sulfide is converted aerobically into elemental sulfur. Subsequently the sulfur is separated and the water is returned to the absorber. Due to the buffer capacity of the washing water, removal efficiencies over 98% are possible. In addition to SO2 removal, it is possible to convert for example other bleeds streams such as scrubber acid or weak acid to sulfur in the same SO2 installation. Recent evaluations concluded that biological desulphurization of flue gases is not only economically attractive in comparison to convention sodium hydroxide scrubbing but also in comparison to gypsum producing systems and even seawater scrubbers. This paper describes the technological and economical viability of biological flue gas desulphurization.

Jan 1, 2005

By E. G. Noble

Microbial leaching is being investigated as a method for recovering the metal values from a domestic low-grade manganese wad ore. Early work showed that heterotrophic microorganisms present in the ore solubilized manganese when cultured in a glucose-mineral salts medium. More recent shake-flask tests using molasses as the sole nutrient source extracted 97 pct of the manganese from minus 300- µm ore in 4 weeks. Column bioleaching with the molasses medium solubilized 99 pct of the manganese from minus 6.3-mm ore in 50 weeks. The results of flask, column, and lab-scale heap bioleaching studies are presented.

Jan 1, 1991

By C. C. Walden, D. W. Duncan, P. C. Trussell

Thiobacillus ferrooxidans released copper from -400-mesh chalcopyrite at a rate of 54 mg/I/hr. Any flotation chemicals remaining on the concentrate did not inhibit the leach rate. Zinc rougher tailings were also leachable. With bacteria, 75 per cent of the zinc and 68 per cent of the copper came into solution. In the sterile controls, only 16 per cent of the zinc and 10 per cent of the copper were released; 100 per cent of the copper and 36 per cent of the zinc were leached from pyrite cinders through the action of bacteria, and 17 per cent of the copper and 10 per cent of the zinc were solubilized in the sterile controls. Less than 0.027 per cent of ~he iron came into solution. The majority of the copper in a converter slag was acid-soluble, but a reverberatory slag responded to microbiological leaching. About 62 per cent of the copper came into solution, compared to 12 per cent in the sterile control. The various factors influencing the rate and extent of microbiological leaching are discussed.

Jan 1, 1966

By T. M. Bhatti

The main purpose of present study was to characterize the dissolution of uranium from low-grade black shale with indigenous isolated strain of Acidithiobacillus ferrooxidans (BSAF-01). The nature of shale is quartzite-schistose and contains uranium content of 0.005% U3O8 (50 ppm U3O8). Uranium is present in the tetravalent oxidation state (U4+) in the shale matrix. The main minerals identified are graphite, quartz, pyrite, mica minerals (phlogopite, biotite, sericite, and chlorite), microcline, K-feldspar and kerogen (hydrocarbon-compounds). Bacterial oxidation of pyrite was an acid-generating system and produced sulfuric acid and ferric sulfate during this biological phenomenon. A series of bioleaching experiments were conducted in shake flasks for leaching of uranium from black shale. The leaching experiments were performed at 50% pulp density using indigenous Fe- and S-oxidizing bacterium (Acidithiobacillus ferrooxidans). Bioleaching data revealed that about 90% ~ 95% U3O8 was leached out from black shale ore. Uranium dissolution from shale depends on pH (pH 1.5~1.9), redox potential (=500 mev) and the concentration of Fe2+ and Fe3+ ions in the leaching environment. The oxidative leaching of U4+ involves a redox reaction with Fe3+ as an oxidant and bacterial re-oxidation of Fe2+ in acidic leaching environment. Uranium leaching efficiency was attributed to the sulfuric acid and ferric sulfate production during bacterial oxidation of pyrite.

Jan 1, 2014

By I R. F MacCulloch

Bacterial oxidation of sulfide minerals is a familiar and commercially available process to enhance gold recovery with problem ores. Pintail Systems, a Colorado, USA based company had developed bio-processes for gold recovery based on natural mineral formation and transformation in a global mineral cycle. The biological recovery of precious metals from ore involves a number of mechanisms that are dependent on the metal-mineralogical association. These processes include: partial bio-oxidation of sulfide ores; oxidation of gangue minerals exposing gold to leaching; surfactant properties of bacteria/nutrient solutions that improve wettability of ores and solution contact with leachable gold and silver; and microbial production and excretion of trace amounts of gold lixiviants, and bio-fracturing or biological alteration of ore minerals. Pintail has demonstrated enhanced recovery of precious metals during cyanide detoxification of spent heaps at the end of mine life. Biological recovery processes also have the potential to be applied to in situ mining technologies. The in situ process application could recover gold from subgrade deposits, small deposits or those ore bodies with uneconomic stripping ratios for conventional mining. In situ biomining can be accomplished at a fraction of the cost of conventional mining and leaching and does not have the environmental liabilities associated with many conventional gold lixiviants.

Jan 1, 2004

By Yu. Gurevich, M. Teremova, I. Prokopev, A. Razvjaznaya, N. Algebraistova

"The objective of this work is the scientific justification and development of efficient and environmentally-friendly method of bulk concentrate preparation for selection with application of microbiological practices. This research suggests to apply Pseudomonas Japonica bacterial culture to the bulk concentrate before the selection circuit in order to clear the surface of sulphides from the xanthate skin. It is also suggested to apply bacterial consortium Ochrobactrum ?nthropi and Pseudomonas aeruginosa JCM 5962 for desorption of diesel residual concentrations. High-efficient and environmentally friendly method of copper-molybdene and lead-zinc bulk concentrate selection was developed based on theoretical and experimental research work with application of microbiological practices. In comparison with conventional methods (steaming, sodium sulphide washing) the above suggested bio-technological method of bulk concentrate preparation before selection cycle will allow to reduce material and power expenditures, and it is also environmentally friendly. INTRODUCTION High-efficient selection of sulphide bulk concentrate is gained exclusively after collecting agent is removed from mineral surface. Therefore, the problem of bulk concentrate preparing before the selection cycle is acute, since the further technological parameters of the subsequent separation depends on the effectiveness of pulp preparation. Existing traditional ways of bulk concentrate preparation. such as washing or steaming, are characterized by high energy and material costs in industrial conditions [1,2]. The microbiological treatment before separation of the bulk concentrate into different kind of concentrates appear one of perspective processes for treatment of bulk concentrates [3,4]. At the present time, the world practice of processing mineral raw materials demonstrates the wide application of technologies using microorganisms: bacterial leaching and oxidation, purification of industrial wastewater. This is due to the fact that biotechnological methods are environmentally safe, low-cost, and suitable for refining complex ores and raw materials of industrial origin."

Jan 1, 2018

By J. D. Isbister

Coal is the most abundant and most economical source of energy in the United States, however, combustion of coal results in release of pollutants to the environment. The release of sulfur dioxide and oxides of nitrogen during combustion of coal contributes to the deterioration of the environment. Energy independence in the United States must include the increased use of coal reserves. Increased reliance on coal for energy will dictate the necessity for making coal a cleaner fuel. New technologies employing a variety of techniques from harsh chemical treatment to mild physical separations to clean coal are rapidly becoming available. Success for any coal cleaning process is in economics which translate into efficient removal of sulfur with high recovery of combustibles as well as low capital and operating costs for the process. Conventional coal cleaning processes remove water soluble sulfates and a portion of the pyritic sulfur and ash from coals. Removal of additional sulfur from coals requires more advanced coal cleaning techniques. Coal contains many organic sulfur forms which are the most difficult of the sulfur types to remove from coal. The heteroaromatic sulfur species, such as the comlex thiophenes, are the most commonly found organic sulfur forms. These sulfur forms are resistant to chemical attack and are considered to be refractory compounds. Atlantic Research Corporation has developed an "unique" microorganism, CB1 (Coal Bug 1), capable of oxidizing thiophenic sulfur in coal to form water soluble sulfates.

Jan 1, 1986

By L B. Sukla, V N. Misra

Microbial desulfurisation of coal has significant advantages over physicochemical desulfurisation processes since the former process selectively removes the inorganic sulfur compounds and heavy metals without significant carbon loss. The purpose of this study was to improve the desulfurisation yield of a coal sample from northeastern coalfields, Assam, India using microbial technique. The coal sample contained 2.13 per cent of total sulfur and 2.59 per cent of ash. Stirred tank reactors of 40 L capacity were operated in batch mode. Initially, the reactor was fed with 40 L of slurry containing ten per cent (w/v) coal, ten per cent (v/v) inoculum of mixed culture of mesophilic acidophiles, native to coal itself and the requisite amounts of constituents for 9K medium without added ferrous sulfate. The percolate of the reactor was then used to seed the medium for the next experiment. The purpose was to obtain a better adapted and more active biomass which would give a better desulfurisation yield for coal. Further studies were conducted in the bioreactor, fed with 40 L of slurry containing ten per cent (w/v) pulp density of coal, ten per cent inoculum (derived from previous studies) and the medium, supplemented with ferrous sulfate. Results showed an increased total desulfurisation yield of 43 per cent in the latter treatment in comparison to the previous one, where the desulfurisation yield was only 23 per cent. The findings also demonstrated the convenience of using inocula derived from coal, where 50 - 60 per cent of pyritic sulfur was removed, while chemical desulfurisation is of little significance with the majority of coal types. The ash content was also reduced to 1.74 per cent as the low pH of the process caused dissolution of a number of common minerals present in the coal.

Jan 1, 2004

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a &apos;reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By Daniel C. McLean

Extraction data for Cu, Zn and Fe were obtained from 4.5" and 10" columns using massive sulfide ore and natural acid mine water. The purpose was to determine if recycling of solution through the column would produce leach liquors of 4 g/l Cu and Zn at extraction rates of 1 g/l per pass at typical flow rates of 0.002 to 0.006 gpm/sq.ft. Test results exceeded expectations. Cu and Zn concentrations of 4 g/l were obtrained within 4 to 6 cycles. Concentrations greater than 6 g/l Cu and 8 g/l Zn were reached within 10 cycles. Concentrations of greater than 40 g/l of Fe and free sulfuric acid were obtained with no decrease in biological activity being observed. No reagents were used.

Jan 1, 1995

By K. A. Natarajan, S. Usha Padukone

"An industrial waste liquor having high sulfate concentrations was subjected to biological treatment using the sulfate-reducing bacteria (SRB) Desulfovibrio desulfuricans. Toxicity levels of different sulfate, cobalt and nickel concentrations toward growth of the SRB with respect to biological sulfate reduction kinetics was initially established. Optimum sulfate concentration to promote SRB growth amounted to 0.8 - 1 g/L. The strain of D. desulfuricans used in this study initially tolerated up to 4 -5 g/L of sulfate or 50 mg/L of cobalt and nickel, while its tolerance could be further enhanced through adaptation by serial subculturing in the presence of increasing concentrations of sulfate, cobalt and nickel. From the waste liquor, more than 70% of sulfate and 95% of cobalt and nickel could be precipitated as sulfides, using a preadapted strain of D. desulfuricans. Probable mechanisms involving biological sulfide precipitation and metal adsorption onto precipitates and bacterial cells are discussed.IntroductionIndustrial effluents from hydrometallurgical and mineral processing operations often contain high sulfate and metal concentrations posing significant disposal problems, which require urgent solution to avoid serious environmental contamination. In such waste liquors, sulfate and heavy metals such as cobalt, nickel, zinc and iron originate from the chemical or biological oxidation of exposed sulfide minerals. Reduction of sulfate and precipitation of toxic metal ions from industrial wastes is essential from the viewpoint of environmentally acceptable waste disposal and recovery of associated strategic metals.Many of these heavy metals are essential for metabolic activity of bacterial cells at low levels. But they exert toxic effects at concentrations encountered in polluted water. Removal of toxic metals through biological reduction of sulfates from industrial waste waters have been practiced for several decades. Metal remediation through common physicochemical techniques such as oxidation-reduction, chemical precipitation, filtration, electrochemical treatment, evaporation, ion exchange and reverse osmosis processes is expensive and not suitable in the case of voluminous effluents containing complexing organic matter and low metal concentrations. Further, strong and contaminating reagents are used for desorption, resulting in toxic sludge and secondary environmental pollution. Biotechnological approaches can be more efficient and cost effective for detoxification of such effluents. Biotreatment/ bioremoval offers several advantages over conventional chemical and physical treatment technologies, especially for diluted and mixed contaminants. Biological detoxification, which involves the use of microbes to detoxify and degrade environmental contaminants, has received increasing attention in recent years (Iwamoto and Nasu, 2001). In addition, valuable metals can be recovered from metal sulfide sludge (Boonstra et al., 1999)."

Jan 1, 2015

By A. L. de Vegt

For the past ten years Paques has been engaged in the development and installation of treatment systems based on biotechnological processes to remove sulfur compounds from water, air and gaseous streams. Metal and sulfate can be removed from mine waters using two biological steps: 1. Sulfate reducing bacteria convert sulfate to hydrogen sulfide (H2S). The H2S reacts with the dissolved metals to form insoluble metal sulfide precipitates. 2. Sulfide oxidizing bacteria convert excess H2S to elemental sulfur. Paques has designed and installed a groundwater treatment system for the Budelco zinc refinery in the Netherlands to remove metals and sulfate as described above. The system has been operating since May 1992 treating a flow of 5000 m /d. A pilot plant started operation in November 1995 at Kennecott&apos;s Bingham Canyon Utah copper mine to develop the processes for metal and sulfate removal from groundwater and selective copper recovery from leach water. The principle of the biotechnological methods, full scale experience, and an overview of the test program at the copper mine are presented.

Jan 1, 1997

R F Johnston 1 ABSTRACT The possibilities for bacterial leaching of refractory gold ores found in the Central Victorian region of Australia are examined. The behaviour of bacteria, especially 77iobacillus ferroaridans is outlined and the effects of these when they are exposed to pyrite, arsenopyrite and stibnite are examined. The factors which are particular to Central Victoria are outlined and the possibility of adapting a bacterial culture to suit the conditions is discussed. It is concluded that a bacterial leaching system is a feasible proposition and that it could enhance leaching rates and yields.

Jan 1, 1994

By Terry I. Mudder

Metal complexed cyanides in wastewaters form as a result of interactions of free cyanide with metals present in the wastewater and exhibit varying degrees of stability, toxicity, and treatability. Thiocyanate, a pollutant commonly found in cyanide bearing wastewaters, is formed through the interaction of free cyanide with sulfur containing species (i. e. pyrrhotite) both present in the wastewater. In certain industrial processes, such as the beneficiation of gold and silver, cyanide is an essential reagent. Since free cyanide, complexed cyanides, and thiocyanate are potentially toxic to humans and aquatic organisms, these compounds must be removed from wastewaters prior to their discharge into surface or ground waters serving as potential potable water sources, marine or fresh water habitats

Jan 1, 1984

Minerals processing operations use a significant quantity of fossil carbon to provide energy and as reductant. Greenhouse gas emissions from the use of this fossil carbon contribute to the global increase in anthropogenic CO2 emissions to the atmosphere. In the spirit of fostering thinking about a step change in this situation, this paper explores opportunities for the use of sustainable carbon from biomass sources in a range of mineral processing operations. The exploration shows that many common processes are contenders for fossil carbon replacement and that feasible scientific research by minerals processing technologists would add to deeper understanding of the potential for a sustainable bio-carbon based industry. It is also shown that there are many dilemmas on the social, environmental and economic fronts to be solved before a biomass based industry could become a reality.

Jan 1, 2004