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By Thomas Fraser, M. G. Driessen

This report is one of a series written by members of the Solid Fuels Mission to Germany describing wartime developments in the mining , preparation, and utilization of coal . The mission was organized early in 1945 under the auspices of the Technical Industrial Intelligence Committee , which cooperated with a counterpart British Committee . Engineers from other allied countries cooperated in some of the investigations . The Solid Fuels Mission operated under the direction of a steering committee headed by Dr. C. J. Potter , deputy solid fuels administrator . The personnel of the mission consisted of H. F. Yancey , in charge , J. W. Buch , Thomas Fraser , L. L. Newman , and L. D. Schmidt , of the Bureau of Mines ; H. H. Lowry , Director of the Coal Research Laboratory , Carnegie Institute of Technology ; H. J. Rose , vice president and director of research , Bituminous Coal Research, Inc .; and F. H. Reed , chief chemist , Illinois Geological Survey . Over 50 reports were written by the members of the Solid Fuels Mission . These and microfilms of supporting data obtained in the course of the investigations are on file at the Bureau of Mines , Washington , D. C. where they are available for public examination . The Office of the Publication Board in the Department of Commerce is prepared to furnish photolith copies , photostats , or microfilm reproductions of all declassified reports . A Bibliography of Scientific and Industrial Reports is issued weekly by the Department of Commerce , Office of the Publication Board , and is sold by the Superintendent of Documents , Government Printing Office , Washington 25 , D. C. , on a subscription basis . An initial payment of 10 dollars will provide for approximately 9 months , and subscribers will be notified when additional remittance is necessary . All subscriptions will begin with volume 1 , No. 1 , unless ordered otherwise . The Bibliography covers all materials and subjects and gives instructions for obtaining the desired items . The reports of the Solid Fuels Mission relate to the following general subjects : Mining methods in the Ruhr district of Germany , with special reference to mechanical cutting and loading equipment , pneumatic packing , and Diesel mine locomotives ; activities of industrial research laboratories supported by the German coal and coke industry ; coal preparation in western Europe ; low-temperature carbonization processes ; metallurgical coke from weakly coking coals ; low- ash electrode carbon from coal ; new developments in the production of metallurgical coke and the utilization of gas and byproducts ; briquetting brown coal and bituminous coal without the use of binders ; recent engineering developments in gas turbines and steam generators , with special reference to use of coal ; German coal-fired heating and cooking stoves; and the commercial extraction of coal with solvents for production of synthetic liquid fuels or chemical products . Numerous reports on the activities of German synthetic - liquid -fuels plants and the plants for the production of synthesis gas from solid fuels are available in the same office as the Solid Fuels Reports . It is planned to publish in this series of Information Circulars the more important reports or combinations of reports prepared by the members of the Solid Fuels Mission . A similar series on synthetic - fuel activities is being prepared .

Nov 1, 1946

By C. C. Stevenson, Thomas Varley, E. P. Barrett, ROBERT H. BRADFORD

The art of treating ores by the chloride volatilization process is still in the experimental stage. The process has not been sufficiently developed along metallurgical lines to warrant a definite statement as to the exact place it will occupy in the industry. The basic theory of the process has received the attention of prominent metallurgists for 20 years, and considerable research and experimental work have been carried on. Much of the experimental work done has never been published; if the accumulated results were made known, they would greatly aid,. the further development of the process. This bulletin aim~ to bring the salient features of the process to the attention of metallurgists for the purpose of furnishing information to and receiving comments from interested parties with the ultimate hope that the process will be a commercial success. If commercially utilized, the process will fill a long-felt want in metallurgy, especially in the treatment of oxidized and semioxidized or" carbonate" ores of copper, lead, and silver. Such ores are difficult to treat by gravity concentration or by flotation: in the former their tendency to slime upon crushing and their being of lower specific gravity than the sulphide minerals cause serious losses; in the latter much has been done in sulphidizing oxidized ores and subsequently recovering the artificial sulphides by flotation. Difficulties in proper sulphidizing and the low recoveries obtained have not balanced the cost of the treatment in many plants and in very few has it proved successful. Evidently there is a big void to fill in the treatment of these ores. No radical changes in present methods are forecast, but it is obvious that chloride volatilization can have a distinct place as a method of treatment for ores that are not readily amenable to present methods. In many plants it might replace concentration methods, especially where part of the mineral content in the ores exists in forms other than sulphides.

Jan 1, 1923

By Paul A. Beck

THE occurrence of the (100) [lOO] or "cube" texture upon annealing of cold-rolled copper has been much investigated.' The conditions favorable for its formation were found to be a high final annealing temperaturez or long annealing time," a high reduction of area in cold rolling prior to the final anneal,' and a small penultimate grain size." The effects of penultimate grain size and of rolling reduction were found by Cook and Richards4 to be interrelated in such a way that any combination of them giving lower than a certain value of the final average thickness of the grains in the rolled material leads to a fairly complete cube texture with a given final annealing time and temperature. Also, according to the same authors, at a higher final annealing temperature a larger average rolled grain thickness, i.e., a lower final rolling reduction, is sufficient than at a lower temperature. These somewhat involved conditions can be understood readily on the basis of recent results obtained at this laboratory. Hsun Hu was able to show recently by means of quantitative pole figure determinations that the rolling texture of tough pitch copper, which is almost identical with that of 2s aluminum: may be described roughly as a scatter around four symmetrical "ideal" orientations not very far from (123) [112]. In the case of aluminum, annealing leads to retain-ment of the rolling texture with some decrease of the scatter around the four "ideal" orientations, and to the appearance of a new texture component, namely the cube texture." A microscopic technique, revealing grain orientations by means of oxide film and polarized light, showed that the retainment of the rolling texture is achieved through two different mechanisms operating simultaneously, namely "re-crystallization in situ," and the formation of strain-free grains in orientations different from their local surroundings, but identical with that of another component of the rolling texture. Thus, a local area in the rolled material, having approximately the orientation of one of the four "ideal" components of the texture, partly retains its orientation during annealing, while recovering from its cold-worked condition, and it is partially absorbed at the same time by invading strain-free grains of an orientation approximately corresponding to that of another "ideal" texture component. The reorientation here, as well as in the formation of the strain-free grains of "cube" orientation, may be described as a [Ill] rotation of about 40°, see Fig. 1 of ref. 6. The preferential growth of grains in such orientations is a result of the high mobility of grain boundaries corresponding to this relative orientation.' " It appears very likely that in copper the mechanism of the structural changes during annealing is similar to that observed in aluminum (except for the much greater frequency of formation of annealing twins in copper). In both metals the new grains of cube orientation have a great advantage over the new grains with orientations close to one of the four components of the rolling texture. This advantage stems from their symmetrical orientation with respect to all four retained rolling texture components of the matrix; they are oriented favorably for growth at the expense of all of these four orientations. As a result, the growth of the "cube grains" is favored over the growth of the others, as soon as the new grains have grown large enough to be in contact with portions of the matrix containing elements of more than one, and preferably of all four component textures. It is clear that this critical size is smaller and, therefore, attained earlier in the annealing process if the structural units, such as grains and kink bands, representing the four matrix orientations are smaller, i. e., if the average thickness of the rolled grains is smaller. Hence, for a given annealing time and temperature, a smaller penultimate grain size and a higher rolling reduction both tend to increase that fraction of the annealing period during which the above condition is satisfied. Consequently, the percentage volume of material assuming the cube orientation increases. The same is true also for increasing time and temperature of annealing when the penultimate grain size and the final rolling reduction are constant, since the average size attained by the new grains during annealing increases with the annealing time and temperature. For the same reason, at higher annealing temperatures a given volume percentage of cube texture can be obtained with larger rolled grain thickness (larger penultimate grain size, or smaller rolling reduction) than at lower annealing temperatures. The well-known conspicuous sharpness of the cube texture may be interpreted as a result of the fact that selective growth of only those grains is favored that have an orientation closely symmetrical with respect to all four components of the deformation texture and exhibit, therefore, a high boundary mobility in contact with each. The effect of alloying elements in suppressing the cube texture, as described by Dahl and Pawlek,' appears to be associated with a change in the rolling texture. For face-centered cubic metals, such as copper, which do exhibit the cube texture upon annealing, the rolling texture is always of the type described above, i. e., scattered around four "ideal orientations" of approximately (123) [112]. The addition of certain alloying elements, such as about 5 pct Zn or 0.05 pct P in copper, has the as yet unexplained effect of changing the rolling texture into the (110) 11121 type. This texture consists of two fairly sharply developed, twin related components. In such cases, as in 70-30 brass and in silver, the annealing texture again is related to the rolling texture by a [lll] rotation of about 30°, however, because of the different rolling texture to start from, it has no cube texture component. At higher temperatures, both in brassm and in silver," grain growth leads to a further change in texture: A [lll] rotation of the same amount, but in reversed direction, back to the original rolling texture.

Jan 1, 1952

By J. E. Hawley

Introduction The Siscoe gold mine is the most easterly producer of gold from deposits lying in the belt of Keewatin and Timiskaniing rocks which extends east from Kirkland Lake, Ontario, and on through the Rouyn copper area. Unlike many of the deposits in this belt, those of Siscoe are contained almost entirely in a stock of much-altered granodiorite which intrudes Keewatin lavas. They are situated on an island of about one square mile in area, lying in lake De Montigny, Dubuisson township, 40 miles south of Amos, on the Transcontinental branch of the Canadian National railways, and 52 miles east, and slightly south, of Noranda. Geographically, the deposits are favour-ably situated with respect to transportation facilities, a through water-route being available from Amos, along the Harricana river and its lake expansions. The deposits consist of auriferous quartz-tourmaline veins of the fissure-filled type and are of particular interest because of their geological structure and genesis. Furthermore, deposits of a similar type occur both in the Keewatin and in granodiorite bodies to the east, in Dubuisson, Bourlamaque, Pascalis, and Louvicourt townships, and it is hoped that the following discussion may be of some aid in the exploration work now being carried on throughout this general area.

Jan 1, 1932

By R Norris, M Dunne

Mining and mineral processing is expected by society and obliged by law to operate in an environmentally friendly fashion, minimising the impact on and avoiding damage to the environment. Substantial efforts by the industry, as well as by process and equipment designers have resulted in many innovative developments, which show that operating in an environmentally responsible manner can be achieved in a cost-effective way. This paper showcases five emerging equipment best practices in industry including installation examples. Flip-flow screening machines are proven worldwide in the dry classification of coal and other minerals, reducing the size of beneficiation plants whilst reducing energy, water demand and media consumption. They also allow the screening of wet/sticky materials not able to be sized using conventional screens. The belt press filter is a small fraction of the operating and capital cost of alternative dry tailings technologies. This gives operators who must dry their tailings a competitive advantage and makes such ægreenÆ operations much more sustainable. The filtercake is disposed with other plant rejects, eliminating the need for tailings dams to be constructed and thus also often increasing mine reserves. Mining applications include coal tailings, sand tailings, sinter plant waste and power station fly ash. Screen-scroll and vibrating centrifuges are widely used in the coal, potash and salt industries to dewater the product to low surface moistures. Inclined plate Lamella separators are used for toxic water clarification and/or sludge thickening in many downstream metal industries with the underflow often dewatered in a belt filter press. Such low cost, high capacity thickeners could also be used instead of conventional thickeners at smaller mines. The simple and reliable continuous washing upward flow (CWUF) sand filters have been used for treatment of waste water from coal preparation plants and steel works as well as in the worldwide production of potable water. The filtered waste water from mining processes can then either be reused or discharged from site. Other installations include cleaning mine water to prevent the blocking of dust suppression spray nozzles.

Jan 1, 2006

By J. F. Adams, V. G. Papangelakis

Chemical modelling is becoming increasingly useful in the development, analysis, design, and control of hydrometallurgical processes. The paper presents the development of reliable databases for chemical modelling of selected hydrometallurgical systems using state-of-the-art software, such as OLI. The modelling strategies are also demonstrated. The high pressure acid leaching (HP AL) of laterites, oxygen solubility in the oxidative leaching process of zinc sulfide, gypsum solubility and lead chemistry in mixed sulfate-chloride solutions are presented as case studies. This on-going work attempts to bridge the gap between theoretical research and industry needs. Computational Analysis in Hydrometallurgy 35th Annual Hydrometallurgy Meeting held in conjunction with the 44th Annual Conference of Metallurgists ofCIM Calgary, Alberta, Canada Edited by

Jan 1, 2005

By G. L. Oldright

This paper is the thirteenth of the series on Smelting in the Lead Blast furnace, and the third of the series on Handling Zinciferous Charges. Two other papers have been written on the Rate of Descent of the Stock Column, and Formation of Accretions. These are Reports of Investigations 2963 and 3094, for the Tooele plant and the Bunker Hill plant, respectively.

Jan 1, 1934

Refractory gold concentrates often contain submicroscopic gold that is encapsulated within the crystal matrix of iron sulfide minerals, such as pyrite, pyrrhotite and arsenopyrite. To recover the gold, the host mineral must generally be broken down chemically by oxidative processes, such as roasting, pressure oxidation or bacterial leaching, which expose the gold for subsequent recovery by leaching in cyanide solution. The focus of attention in these pretreatment processes is usually the oxidation of the sulfides to elemental sulfur, sulfur dioxide gas or sulfate ions. Less attention is paid to the deportment of iron and the changes in its oxidation state, although this can have a profound effect on gold and silver liberation, as well as downstream operating costs. Iron sulfide minerals break down completely during pressure oxidation, and dissolve in the sulfuric acid solution that is gener-ated from oxidation of the sulfides. This dissolution liberates the tiny gold particles that were originally trapped in the sulfide crystals, and gold recovery during subsequent cyanidation is usually very high (>95%). Iron goes into solution in the oxidation process, initially as ferrous sulfate, but this compound is rapidly oxidized to ferric sulfate, which then hydrolyzes and reprecipitates. The form of the precipitate varies depending on the operating conditions in the autoclave and the presence of certain metal cations. When the acidity in the autoclave is quite low (<20 g/L H2SO4) and the temperature is high (>200°C), the formation of hematite is favored. When the acidity is high (>20 g/L H2SO4) and the temperature is relatively low (160 to 200°C), the formation of basic iron sulfate is favored. If the ore or the leach solution contains significant levels of certain cations (such as Na+, K+, NH4+, Ag+ or Pb2+) and the acidity is high (>20 g/L H2SO4), jarosite compounds are favored. Hematite is the desired iron product in the autoclave discharge, for both metallurgical and environmental reasons, but it is difficult to operate an autoclave under the conditions required for effective liberation of gold without converting some of the iron to basic iron sulfate and/or jarosite. These compounds fall into a category of iron compounds known generically as iron hydroxy sulfates, all of which can cause significant processing and environmental problems in the downstream gold process. This paper deals specifically with basic iron sulfate: the conditions under which it is formed in an autoclave, the problems that are caused by its presence in the feed to a cyanidation plant and possible remedial strategies that can be adopted, both in the autoclave and downstream.

Jan 1, 2010

By Paul M. Tyler

Calcium chloride is a conspicuous example of a former waste product that has found a place for itself in the onward march of civilization. Formerly considered a troublesome constituent of the effluent sewage of many chemical manufacturing plants and salt works, it has now become a commercial product of substantial importance, with sales aggregating almost six million dollars in 1929. The point has not yet been reached where it would seem profitable to undertake large-scale production of calcium chloride as a main product, but as a byproduct it has become an item that warrants serious consideration by all who are in a position to recover it at sufficiently low cost. The largely increased demand for bromine and for certain magnesium salts, which are likewise potential byproducts associated with calcium chloride in most salt-works bitterns (and brines generally), adds further impetus to commercial research directed toward the fuller utilization of the natural saline resources of the United States.

Jan 1, 1934

By K. Janghorban

Multilayered ceramic-metal composites were produced by solid state diffusion bonding of polycrystalline alumina and three Al alloys containing 1 to 2%Sr, 2% Mg and Mg + Si (5057 Al alloy), The multilayered structures were fabricated at 610°C under a compressive stress of 3 MPa for 2 hours in He-5%H atmosphere, The ceramic-metal interfaces were studied by SEM and TEM equipped with energy dispersive spectrometer (EDS). Addition of 1 wt % Sr to Al promoted good adhesion, without producing any interfacial products, while the Al-2%Sr was poor in this regard due to the presence of dispersed A14Sr which is an intrinsic phase in the Al-Sr phase system, The Al-2%Mg alloy produced a continuous film at the interface, which was characterized to be MgAl2O4. Al alloys containing Mg and Si (5057 commercial alloy) produced not only the spinel structure (MgAl2O4), but another phase rich in Mg and Si (close to Mg2Si), These latter interfacial reaction products were not the intrinsic phases in Al-Mg alloys, and were reaction products at the Al2O3 ?Al alloy interfaces.

Jan 1, 2005

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide&apos;s smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates &apos;CSO or CSC&apos; under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements&apos; chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

The purpose of this paper is to present the methods used in ground water control and the considerations that affected the development of these techniques. Production at Knob Lake is currently proceeding at depths which may be as much as 200 feet below the original standing water table. In order to produce a more saleable product and to improve operating and maintenance conditions, it is necessary to depress the water table below the mining level. Considerable success has been achieved by drilling deep wells in strategic locations and installing vertical tur-bine pumps at depths of up to 400 feet. This method is especially suitable for operation under severe winter conditions and has reduced the detrimental effects by a far greater extent than other methods of water control, Spring runoff is handled in open sumps, but all other water from four mines, with flows exceeding 16,000 g.p.m., is pumped all year &apos;round from about thirty-five wells. T HE Knob Lake operation of the. Iron Ore Company of Canada is located on the Quebec-Labrador border, 320 miles north of Sept Iles,

Jan 1, 1965

By D. W. McDonald, N. A. Duke, R. L. Hauser

"Abstract- The NERCO Con Mine is situated in the amphibolite facies aureole of the Western Plutonic Complex overprinting the Yellowknife Greenstone Belt. Metamorphic grade of the upright monoclinal basaltic succession decreases from hornblende-amphibolite facies along the border of the batholith to greenschist facies. Metamorphic isograds, subparalleling the faulted margin of the batholith, transect volcanic stratigraphy and coincide with major gold­ bearing shears.Gold mineralization is confined to north-striking, west-dipping shear zones where hanging­ wall amphibolite facies mineral assemblages retrogress to chlorite-carbonate-sericite-sulfide bearing schists hosting multiple generations of quartz-ankerite veins. The gold-producing portions of the Con and Campbell Shears occur where these structures transect an east trending thermal corridor. The corridor is defined by granitic plugs and a number of related breccia bodies, that can be traced outwards from the batholith across the greenstone belt.Prograde reactions of greenstone during amphibolitization effectively liberate fluids that partition metals. With retrograde reactions at shear zones, gold is precipitated with quartz due to the destabilization of sulfide and arsenic complexes. The coupling of regional prograde metamorphic and restricted retrograde metasomatic overprints suggest mineralization is temporally related to emplacement of the Western Plutonic Complex. Economic gold concentrations within the intrusive corridor indicates enhanced metamorphic overprint of hornfelsed greenstones enveloping satellite intru sives peripheral to the main batholith."

Jan 1, 1993

By N. Menad

Thermal treatments of five different types of non-ferrous metallurgical wastes, under controlled atmosphere, were carried out at temperatures lower than 800 °C. The aim of these treatments was to reduce the toxic elements content and to increase that of valuable metals in the residue. <Best results were obtained by their treatments in air or hydrogen or successively both of them. Simple treatments using air or hydrogen of three samples allowed the elimination of more than? 95 % of their toxic elements and&apos; almost doubled their valuable metals&apos; concentration. For the rest two samples, combined treatment was necessary for their efficient decontamination and the concentration of valuable metals, in the treatments residue, to a reasonable value. Most of the solids issued from these treatments can be recycled in .the current non-ferrous metallurgical processes.

Jan 1, 1995

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By S. Haggarty, R. Walton

Barrick&apos;s growth and development plan will add three major new mines during 2005 including the Lagunas Norte Project in the La Libertad Province of Peru, the Veladero Project in the San Juan province of Argentina, and the Tulawaka Mine in north¬western Tanzania. Lagunas Norte and Veladero are similar in that they are both green-field open pit deposits at elevations over 4,000 meters above sea level, with two stage crushing and heap leaching followed by Merrill Crowe zinc precipitation for precious metal recovery. Operating sites will each generate in excess of 700,000 ozs Au per annum with commissioning and full scale operation planned during the third and fourth quarter of 2005. Details with regards to regional geography, development schedule, production and process specifics for Lagunas Norte and Veladero will be discussed in this presentation providing an overview for the respective properties.

Jan 1, 2005

By R. C. Dunne

As ore grades of existing and new ore deposits continue to decrease there is ever increasing pressure to decrease operating costs to maintain profitabitabitiy at existing mine sites and for new projects. The accepted solution to this dilemma in most cases is to increase treatment rate, leading to a coarser grind, at the expense of marginal decreases in recovery. The recovery loss is usually associated with losses of liberated and composite coarse material. This paper will review the practice of coarse particle flotation, including the reagent chemistry, cell hydrodynamics, froth stability, entrainment and flotation cell design, all parameters important to the recovery of coarse liberated and composite particles. This will provide a better understanding of opportunities to improve the recovery of coarse particles. Some examples will be provided.

Sep 1, 2012

By R. S. Krarner

Fly ash, a by-product of coal burning power plants, poses a major problem for the utility industry since most fly ash must be landfilled. These quantities may represent as much as 20% of the total material going into landfills. A major problem with fly ash utilization is that although the ash consists of useable components, ash composition can vary depending on the types of coal burned and plant operating conditions. Ash is first characterized using SEM, image analysis, and chemical methods. Processing techniques were developed to separate ash into various components including cenospheres, magnetic spheres, carbon, and clean ash. These products are again evaluated for various utilizations before being used to produce valuable products such as mullite, activated carbon, fillers in plastics, and concrete.

Jan 1, 1994

By R. Shimpo

Equilibrium calculations by a computer may sometimes fail in giving solutions when the system includes a large number of components and more than three phases, and especially when no definite information about stable phases is given. An improved method of calculation is presented in which the number of phases need not to be initially fixed, phases can appear or disappear in the course of&apos; calculation and a new method is combined with the Newton-Raphson method to obtain solutions easily. The improved method is applied to the copper smelting operation and all the successive stages of the operation are successfully simulated.

Jan 1, 1983

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) measurements on solutions and isolated powders provide direct evidence for the involvement of Cr(V) species in the reduction of Cr(VI) by NAD(P)H. ESR analysis of an isolated Cr(V)NAD( P)H solid yields 6 11 = 1.9831 and 6.i. = 1.9772, indicating that the unpaired electron occupies the d22 orbital of the Cr(V) ion, with square-pyramidal geometry. Addition of hydrogen peroxide (H2 0 2 ) to the N AD(P)HCr( VI) reaction mixtures suppresses the Cr(V) species and generates hydroxyl (""OH) radicals. The ""OH radicals were detected via ESR spin trapping, employing 5,5-dimethyl-1-pyrroline-N-oxide and a-(4-pyridyl-1- oxide)-N-tert-butylnitrone as spin traps. The dependence of Cr(V) and ""OH radical formation on the H20 2 and Cr(VI) concentrations indicates that the Cr(V) species react with H20 2 to generate the ""OH radicals. Similar results were obtained by using various diols (arabinose, cellobiose, FAD, fructose, glyceraldehyde, ribose, and tartaric acid), a-hydroxycarboxylic acids, and glutathione. Investigations with superoxide dismutase showed no significant participation of 02 in the generation of OH radicals. These results thus indicate that the Cr(V) complexes, produced in the reduction of Cr(VI) by cellular reductants, react with H20 2 to generate ""OH radicals, which might be the initiators of the primary events in the Cr(VI) cytotoxicity.In this paper we report an electron spin resonance (ESR)3 spectroscopic detection of Cr(V) species in the reduction of potassium dichromate, henceforth called Cr(VI), by NAD(P)H and other diols. Also reported here is the detection of the hydroxyl (""OH) radical in the reaction between hydrogen peroxide (H2O 2) and a variety of Cr(V) complexes. This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step m the mechanism of Cr(VI) toxicity, mutagenicity, and DNA alteration, the details are not yet clear (1-5).Earlier studies on the mechanism of Cr(VI) reduction in cellular systems include those on the reduction of chromate by microsomes (6-8), rat liver DT-diaphorase (9), and aldehyde oxidase (10). All these studies imply that Cr(VI) can be reduced to Cr(Ill) by cellular constituents. Regarding the mechanism of Cr(Vl) carcinogenicity, Jennette postulated that Cr(V) is the ultimate carcinogenic form of chromium compounds (8). This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions (11-33). More recently, however, Kawanishi and co-workers (34) have investigated the mechanism of DNA cleavage induced by Cr(VI) in the presence of H20 2 and have argued that it is not Cr(V) itself that is carcinogenic, but it is the reactive oxygenated species (02, 10 2 , ""OH) (produced by the decomposition of the Crv(02) ¾ - ion) that cause the DNA alteration."

Jan 1, 1990