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By Alcy Dias Rodrigues

O Centro de Operações do Sistema Elétrico da Aperam South América possui um sistema de automação chamado SAE (Sistema de Automação de Energia) para realizar a distribuição e operacionalização da Energia Elétrica na planta em Timóteo, sistema este com mais de 20 anos de implantação. Devido ao alto grau de obsolescência do sistema SAE, a dificuldade de se atualizar todos os componentes do sistema e a complexidade e dificuldade do acesso aos dados, verificou-se a necessidade de encontrar uma forma de disponibilizar os mesmos para os demais sistemas da empresa. Com base nestas necessidades, foi desenvolvido e implantado um GATEWAY capaz de realizar a comunicação com todas UTR’s CORTEX (remotas do sistema), através do protocolo CONITEL 2020, disponibilizando estas informações coletadas em uma camada OPC SERVER para que o sistema PIMS (Sistema de Gerenciamento de Informação da Planta) realize a coleta e armazenamento destas informações, permitindo assim um melhor gerenciamento de energia pelo VIRIDIS (Sistema de Gestão da Eficiência Energética utilizado na APERAM), além de permitir que toda a planta tenha acesso em tempo real às informações de tensão e corrente de todo setor de 13,8 kV, 69 kV e 230 kV.

Oct 30, 2017

By Drew Bazil, David Smith, Matteo Ferrucci, David Pittman

The Gateway program will provide additional rail capacity between New Jersey and Manhattan. This paper describes how a 70-foot-deep section of cut and cover tunnel was designed to directly support future high-rise towers. The tunnel will link previously completed tunnel sections under Hudson Yards to future tunnels under the Hudson River. The design aims to minimize constraints on future overbuild and future tunnels, while maximizing constructability within a small worksite. The tunnel will pass under the High Line elevated walkway, next to an active rail yard, and close to a subway tunnel. The design was developed by a tri-venture of WSP, STV and AECOM. WSP led the design of major underground works; STV designed utility relocations and the underpinning concept for the High Line; and AECOM designed temporary in-tunnel systems. Construction is expected to start in 2023.

Jun 13, 2023

By D. W. Rich

An environmental management system (EMS) is a key part of a company?s environmental stewardship. Procedures and practices to continually improve environmental performance can provide great benefits in operating the company. Managing site environmental quality data is a key component of this. An environmental data management system (EDMS) is an important element of the EMS for mining and other projects, providing project staff with the information that they need to make decisions that can have a significant impact on public health. Improvements in computers, data communications, and transfer formats have made it much easier to implement an integrated EDMS program for gathering, managing, selecting, and displaying data from the field and the lab. Software now lets users define sampling plans, create files for field data entry, and print Chains of Custody. Laptop and handheld computers facilitate field data entry and may provide automated communication back to the office. Most labs can now create usable electronic data deliverables. QC checks and limit comparisons can be largely automated. The result is organized data that can be efficiently used for reporting, graphing, and mapping, to better understand project issues.

Jan 1, 2009

By Ron Tluczek

[Power Point Presentation]

Jan 1, 2006

By J. Weyer

"Colored gemstones are most often mined in small scale artisanal mining operations. Sri Lanka is well known as source for precious stones since thousands of years. Gemstones are mine in small open pits, directly in rivers (river dredging) and in underground mines. Almost all mined deposits are alluvial deposits. PRECIOUS STONES AND DEPOSITS Precious stones from Sri Lanka are well known for thousands of years. Tales and legends from Arabia, India, China and reports from discoverers like Marco Polo describe the fabulous stones from Ceylon which was the name for Sri Lanka before 1972. Already 1000 BC King Salomon got valuable gemstones from the legendary Queen of Sheba on her visit to Jerusalem. Paintings (frescoes) of the “cloud maidens” with huge gemstones can be seen at the “mirror walls” of the Sigiriya rock fortress - one of the eight World Heritages Sites of Sri Lanka.And even today some of the most valuable and most desired gemstones come from Sri Lanka. The term “Ceylon Sapphire” stands for an excellent royal blue color of high quality corundum from Sri Lanka. Reason enough to look a bit closer how these gemstones are mined. Sri Lanka has rich gemstone deposits which are mined underground, in small open pits or directly within a river. Some of the primary deposits in magmatic and metamorphic rock are also known, but most gemstones are mined in secondary alluvial deposits. Gem bearing deposits can be found in a band from NW to SE. Highly probable deposits and main mining areas can be found around Ratnapura – the city of gems, down to the coast (Matale) and up to the region around Elahera. These secondary deposits are mostly thin layers of gravel and sand, so called “illam”. The depth can vary between some dm to 10 25 m or even almost 40 m. But the average depth is about 12 m. Gemstone mining is controlled, licensed and regulated by a special authority – the National Gem and Jewelry Authority - which was founded in 1993. Another task of this authority is the promotion and development of the gemstone industry and the control of import and export of gemstones. Any violence of the NGJA law can lead to a fine or even up to 5 years imprisonment. To increase the confidence in the gemstone industry the Authority offers a unique service to foreigners. All bought gemstones can be tested free of charge in certain laboratories in Ratnapura and Colombo. So visitors can be sure they got no imitations, wrong stones or even synthetic stones or glass. It was said that detected synthetic stones will be destroyed and the seller will do all he can to replace the stone with the right stone. Otherwise he will lose his license."

Jan 1, 2016

By R. L. Stanton

"The present contribution examines, in some detail, what appear to be the three outstanding features of the field occurrence of the conformable ""pyritic"" deposits. These are their association with fragmental volcanic rocks (and derivatives), their occurrence in sediments of near-shore formation, and their highly variable structural associations.In a recent paper it has been suggested that two such ""pyritic"" de-posits in New Brunswick may have originated as marine concentrations of volcanic base metal and sulphur compounds, and that many of their present features are the result of diagenesis, folding, and regional metamorphism. This is now put for-ward as a general explanation for the particular class of deposit considered.Such deposits should, on this hypo-thesis, be regarded quite simply as an integral part of the particular geological environment in which they occur -as a normal, though minor, sedimentarry type developed, char-acteristically, in near-shore and shelf facies of intravolcanic units formed along the margins of eugeosynclines. They should not be considered -as, for example, is required by the re-placement theory -as later features simply superimposed on a geological situation to which they are genetically unrelated. Where they are associated with folds and other structures, this may be attributed, from one in-stance to another, to mechanical migration during folding, weaknesses induced by pre-existing sulphides, and, occasionally, to fortuitousness.In the light of this postulated origin, it is suggested that the first stages in regional prospecting for deposits of this particular class should be broadly palaeogeographical. Later phases of the search should then be directed to the delineation of sedimentary facies and, finally, to the investigation of geological structure."

Jan 1, 1960

By J. F. Wright

Introduction Previous to 1924 the mining fields of Manitoba and adjoining territory had not been prospected in detail, and the reports of the exploration of the mineral discoveries to that date had been discouraging. As a result of the apparent failure of all the mining operations, some considered that geological conditions in the country westward from lake Superior extending across western Ontario, eastern and northern Manitoba, and northern Saskatchewan, were different from those in the northeastern part of Ontario, where large gold mines had been developed. Discoveries of importance thus were necessary to renew interest in the mining possibilities of this part of the Canadian Shield, and the successful operations at Flin Flon and Howey in large part were responsible for the beginning of the present activity in what may be described as the part of the pre-Cambrian Shield within central Canada. In Manitoba, the more important developments at present are in the Central Manitoba, Gods Lake, and Knee Lake fields. The large area from west of Flin Flon east to Herb Lake, also, is being explored carefully for gold deposits of merit. A number of properties in Red Lake, Woman Lake, and Pickle Crow areas are being drilled and explored underground. Many of the mines of the Lake of the Woods area, that were producing gold 30 years ago, are re-opened, and new prospects in this field and in the country to the east are being explored. The recent development of Little Long Lac mine in an area near the railway, and considered by some to have been thoroughly prospected years ago, has stimulated interest in the areas formerly prospected. In the autumn of 1934, the belts of greenstone and sediments in the country east of lake Nipigon were staked, and deposits in these fields will be explored in detail this year. This paper is presented to discuss the general features of the geology and gold deposits of the various prospecting fields in Manitoba and adjoining territory. Details of a number of the areas and mines will be presented at this meeting in papers by Barton on Little Long Lac, Tanton on Sturgeon River, Baker on Gods Lake, and Brownell and Kinkel on Flin Flon. Although mining was not active in most of this territory previous to 1930, geologists of the various government departments continued field studies and interesting reports were issued.

Jan 1, 1935

By AIME AIME

ON the morning of Monday, Nov. 9, 1936, two motorcycles, with sirens screeching, - escorted a procession of 70 automobiles from the Colonia Railway Station in Mexico City to the Hotel Geneve. Riding in' the cars were just over 200 visitors- members of the A.I.M.E. and their guests. They had come, via St. Louis, in two special trains from 24 different states for the 146th General Meeting of the Institute. During the morning they and 200 others, who had come from the United States by automobile or from various cities and mining camps in Mexico, duly registered with !efficient Mme. Irma Ordoiiez de Obregon and her assistants. Then started a week of strenuous but delightful activity that will never be forgotten by the participants. They were to cover more than 500 miles by automobile, always with a motor escort, and often

Jan 1, 1937

By Norman A. Grant

"Location and Transportation FacilitiesTHE BEAVERLODGE area of North Saskatchewan is on the north side of lake Athabasca, 500 air miles northeast of Edmonton.The main Eldorado operation and townsite are on the north •side of Beaverlodge lake, which is immediately north of lake Athabasca and is separated from it by only a mile long portage at Lodge bay. The once famous town of Goldfields. Saskatchewan, and the Box property of the Consolidated Mining and Smelting Company of Canada, Limited, are located on lake Athabasca nine mines from Beaverlodge townsite.Previously, all Eldorado freight was delivered by barge at the Lodge Bay portage, hauled across the portage, and across Beaverlodge lake by small Northern Transportation Company barges, which involved many handlings.In 1952 the port of 'Bushell' was established at Black bay. This is a particularly snug harbour, well protected from the main body of the lake and with good foundations for docking facilities. A Butler building, 300 ft. by 60 ft., and tank farms provide storage at the port. A •road from Bushell to the main Beaverlodge operation, a distance of twelve miles through rugged terrain, was built by the Saskatchewan Government. The cost was shared by the Saskatchewan Government, the Federal Government, and Eldorado and other mining companies.Along this road are located the properties of several enterprising mining companies and near the midpoint lies the ambitious budding town of Uranium. This road has made portaging unnecessary and palletized freight loaded at Waterways, Alta., is now loaded directly on trucks at Bushell and delivered to the point of consumption."

Jan 1, 1953

By Wilbur I. Duvall

This paper discusses general principles of underground opening design based on the concept that with the necessary input data regarding the geology of a site, the physical properties of the rocks, the in situ stress field in the rock and the general geometry of the underground openings, the rock formation can be classified into six major categories which are useful for design purposes. Using simple theories for the criteria of failure for rock In compression and tension, general elastic theory for stress concentration around openings and In structures, beam theory for stability of roof rock, and elementary inelastic theory for creep phenomena, basic design techniques are outlined for the various rock classifications. The need for field evaluation of the theoretical design is stressed and some general techniques that should be used in these field evaluations are discussed. Where appropriate, the need for additional studies and research is noted.

Jan 1, 1977

By Tim Chapman

This general report considers what promoters of deep basement projects want from their teams and whether they get it often enough. Most large projects are based on complex financial models where the funding is related to a future income stream. Project delays and cost over-runs can critically affect the financial model. Too often, delays and cost over-runs originate in the substructure and foundations. We must take positive steps to improve our industry's reputation for reliability.

Jan 1, 2006

In the past two and a half years, over 40 000 metalliferous mining and related services personnel have been trained through an Australian Generic Safety Induction system. This is almost half of AustraliaÆs metalliferous mining related workforce. This remarkable industry acceptance and delivery of safety courses is supported by Acacia Resources, Great Central Mines, Homestake, Newcrest Mining and WMC Resources, amongst hundreds of other mining, exploration and major contracting and services companies. MARCSTA; the Mining and Resources Contractors Safety Training Association (a pro-active not-for-profit self-help group of 24 major contracting companies) developed this generic safety induction. MARCSTA set out to find the æcommon groundÆ necessary to help address the evident safety problems and cost of re-training that were plaguing development of an internationally competitive and productive export industry. The incredible expansion of Australian mining during the decade fuelled a need for out-sourcing, resulting in much larger numbers of contractors on-site. At the same time, changes within Australian legislation, community expectations and the development of huge fly-in/fly-out operations and widespread skills shortages led to a rapid labour turnover and a higher paid workforce. Many Australian mining houses also ran international operations, particularly in South East Asia and head hunted people across the world. The skill levels fluctuated and fell at some local operations. Employers could no longer rely on systematic in-house training of permanent employees to improve safety and productivity as workers could and often did move on. Serious discrepancies in both quality and quantity of safety induction training and work practices occurred. Repetitive, boring and ineffective safety training became an embarrassing and costly burden for companies and workers alike. Then a spate of mining deaths sparked highly publicity, workforce concern and a demand for improvement from government, unions and corporate stakeholders. MARCSTA recognised it had to develop a high-quality safety-training program to satisfy the needs of all employers and be acceptable to others within the industry. This induction system had to be flexible enough to meet differences in legislation between states and industry sectors and be portable to enable cost and time savings for the new transient workforce. Changes in the last two years as a result of evaluating and incorporating various Taskforce inquiries into underground mining fatalities later led to the development of the MARCSTA Underground Safety Induction. This logical development added to the run away success of MARCSTAÆs General Safety Induction and was seen to be essential for many surface mines that were planning to develop underground operations. There are many lessons that MARCSTA learnt during its development that Pacific and South East Asian mining operations can benefit from. The most important of these are the support of stakeholders within industry and the recognition of higher safety and health expectations from workers and government. This goes hand-in-hand with the productivity and return on investment expectations of companies and their shareholders.

Jan 1, 1999

There's a right way and a wrong way to store diesel electric systems and similar equipment for generating on-site power, according to James Frankow, service manager for Allis-Chalmers Corp's Engine Division. In any event, the less storage the better. Many generating sets are stored before installation, especially when new construction is underway. Improper storage, or mothballing, can create initial reliability problems. Therefore; arrange for inside storage with no drastic extremes in temperature or humidity. If engines and alternators are stored in areas other than inside a dirt-free and temperature-controlled building, the unit or engine should be completely covered and protected against the environment. Before covering it with a canvas or with plastic, the unit should first be sealed at the following critical engine openings:

Jan 3, 1978

The common approach of designing blasts on a trial and error basis is quickly coming to an end. When utilizing the full scale blast environment, trial and error can quickly become cost prohibitive and leaves much to be desired in terms of true blast diagnostics. In these situations testing is usually only continued until a perceived improvement is achieved and when the gross undesirables in blast results are removed. This does not preclude, however, that further improvements of up to 100% or more can not be obtained.

Jan 1, 1994

The common approach of designing blasts on a trial and error basis is quickly coming to an end. When utilizing the full scale blast environment, trial and error can quickly become cost prohibitive and leaves much to be desired in terms of true blast diagnostics. In these situations testing is usually only continued until a perceived improvement is achieved and when the gross undesirables in blast results are removed. This does does not preclude, however, that further improvements of up to 100% or more can not be obtained.

Jan 1, 1991

The common approach of designing blasts on a trial and error basis is quickly coming to an end. When utilizing the full scale blast environment, trial and error can quickly become cost prohibitive and leaves much to be desired in terms of true blast diagnostics. In these situations testing is usually only continued until a perceived improvement is achieved and when the gross undesirables in blast results are removed. This does does not preclude, however, that further improvements of up to 100% or more can not be obtained.

Jan 1, 1991

By J E. Everett, K Jupp, T J. Howard

Simulation modelling is a practice commonly used in the mining industry to evaluate alternative process designs. Such modelling is typically undertaken as an optimisation study to increase the efficiencies, productivity and product quality of operating mines. In this situation, real short-term grade variability data of extracted ore are available from production records as input data into the simulation.There is also a need for simulation modelling to be performed before mines are approved for construction to clarify the grade variability characteristics that can be expected from the operating mine and assist in the optimisation of the process design. In this situation no historical short-term grade variability data are available. To achieve meaningful and reliable results from a simulation it is necessary to have input data for the ore to be extracted from the pits, representative of the short-term grade variability that would be expected for the operating mine.This paper describes an example of a path taken to generate realistic input data.A method described as composite cut-off criterion was used to distinguish ore from waste, which gave substantially greater recovered tonnage at target grade compared to the conventional quadrant cut-off grade criteria.The only data available for the project was resource model data in the form of kriged block models, which are known to underestimate true ore grade variability. To achieve realistic results from the simulation it was essential to increase this variability while maintaining the accurate average grades. Areas of certain deposits that were modelled using both kriging and conditional simulation estimation techniques were quantitatively compared to establish the comparative variance and the kriged data was modified to match the conditionally simulated variance.A realistic mining model was generated via a process of discretisation and regularisation of the resource blocks. Quantitative assessment demonstrated that this method adequately compensated for ore dilution and that adjustment for ore loss was not required due to an ore skin surrounding the edge blocks.The conditioned data was then used to generate a schedule of daily mine extraction, considering grade variability, tonnage, equipment constraints and extensive blended-in-blended-out precrusher stockpiles to feed into the process design simulations.For the precrusher stockpiles a number of alternative allocation criteria were examined for ore being extracted from the pits to identify the best method in achieving reduced variability through the daily scheduling system. The study concluded that a single analyte separation criterion produced acceptable variability with minimal complexity.The blending efficiency of manually stacked and reclaimed precrusher stockpiles was studied to determine a realistic blending efficiency within the pile. A recommended method of building and reclaiming was determined to give maximum blending efficiency.Finally, the data was used as input into process design simulation models; simulation from crusher feed to shiploading demonstrating that control of shipment grade variability was achievable and that the conditioning of the data delivered realistic results.CITATION:Jupp, K, Howard, T J and Everett, J E, 2013. Generating synthetic data for simulation modelling in iron ore, in Proceedings The Second AusIMM International Geometallurgy Conference (GeoMet) 2013 , pp 231-238 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Sep 29, 2013

By R. V. Ramani, J. Qin

"During the mining process, the insitu material is broken into different size ranges, from very, large pieces to very fine particles. Some of the fine particles become airborne. In underground coal mining, airborne respirable. dust is associated with health and safety of the miners: The amount and size distributions of airborne dust are important parameters to effective dust control measures. The design of underground mine experiments, including sampling procedures and sample analyses methods to determine these parameters are presented in this paper.. A total of fifteen continuous miner cuts were sampled. The amount of dust generated during the cutting process and the relationship between total and respirable airborne dust concentrations and amounts are examined.The amount of respirable dust airborne is on the average only. 0.016% of the respirable dust generated. On the average, 61% of the total .airborne dust measured is in the respirable size range. The amount of respirable airborne' is on the average 36% of the respirable size fraction in the total airborne dust. For equal proportion of rock and coal material cut, rock contributes about twice as much fines (<0.22 mm) as coal. Additional fundamental research is necessary to further the understanding of 'the airborne propensity of respirable dusts in mine atmospheres.INTRODUCTIONMining is a sequential process of breaking, gathering, loading, and transporting the in-situ .materials.' In underground coal mines, duet in both the non-respirable and respirable size ranges is generated and entrained in every phase of the process. Even though large amounts of dust particles' adhere to run-of-mine coals, part of the dust generated becomes airborne (Cheng and Zukovich, 1973). Studies have shown that bit type affects the amount of dust generated'(Evans and Pomeroy, 1966; Kurth et al., 1975; Roepke et al., 1976; Stecklein et al., 1982; and Khair and 'Reddy, 1986). Deep cutting can reduce airborne dust generation (Black and Schmidt, 1977 arid, Black et 1978). Mechanical properties of. coal seams are also important factors in dust generation. Laboratory studies have shown that Hardgrove Grindability Index (HGI) of the coal has a relationship with the amount of respirable. dust generated (Beafi and Ramani, 1979; Moore and Bise, 1984; and Moore, 1986). However, these relationships have not yet been validated with' data from the mines. The amount of dust airborne depends on a number of factors. Suppression of the airborne propensity of dust by water sprays is'widely practiced and is very effective. Water flow rate; pressure and configuration of water sprays have been identified as major factors affecting dust capture by sprays (Courtney and Cheng, 1977; Courtney et al., 1978; and Kissell et al., 1979). Ventilation is a very important means of controlling the dust level at the coal face (Jayaraman, 1977). According to a National Academy of Sciences study (1980), the mechanism of dust generation and the process by which the generated dust becomes airborne are complex and not yet completely understood coal seams are also important factors in dust generation. Laboratory studies have shown that Hardgrove Grindability Index (HGI) of the coal has a relationship with the amount of respirable dust generated (Beafi and Ramani, 1979; Moore and Bise, 1984; and Moore, 1986). However, these relationships have not yet been validated with data from the mines. The amount of dust airborne depends on a number of factors. Suppression of the airborne propensity of dust by water sprays is widely practiced and is very effective. Water flow rate; pressure and configuration of water sprays have been identified as major factors affecting dust capture by sprays (Courtney and Cheng, 1977; Courtney et al., 1978; and Kissell et al., 1979). Ventilation is a very important means of controlling the dust level at the coal face (Jayaraman, 1977). According to a National Academy of Sciences study (1980), the mechanism"

Jan 1, 1989

By N. S. Dalal, V. Castranova, X. Shi, W. Wrr, V. Vallyathan

"SUMMARY Data presented here indicate that freshly fractured silica exhibits surface characteristics and biologic reactivity distinct from aged silica, and on this basis we propose that these surface features may lead to enhanced manifestations of lung Injury. Grinding of silica produces ~10"" Si and SI-O (silicon-based) radicals per gram of dust on the particulate surface which are characterized by an electron spin resonance (ESR) spectrum centered around g = 2.0015. These silicon-based radicals react with aqueous media to produce OH radicals, which are demonstrable using a DMPO spin trap. The concentration of silicon-based radicals in silica decreases with aging in air and exhibits a half-life of ~30 h, whereas its ability to generate OH radicals in aqueous solution decreases with a half-life of ~20 h. However, on storage in aqueous media, the concentration of silicon-based radicals end the dust's ability to generate OH radicals decrease significantly within a few minutes. Freshly ground silica is also more biologically reactive than aged silica, because freshly crushed silica activates a greater respiratory burst In alveolar macrophages than aged silica, i.e., storage of ground dust in air decreases silica-Induced superoxide anion secretion, hydrogen peroxide release, and NBT reduction by 25%, 68%, and 43%, respectively. Furthermore, compared to aged silica, freshly ground silica exhibits a greater cytotoxic effect on cellular membrane Integrity, i.e., a 1.5-fold increase in LDH release from macrophages, a 36-fold increase in hemolytic activity, and a three-fold increase in the ability to induce lipid peroxidation. Because acute silicosis is frequently associated with occupations in which freshly fractured crystalline silica of respirable size is generated, the present study suggests that fracture-generated silicon-based radicals may play a significant role in the pathogenesis of this disease. AM REV RESPIR DIS 1955; 133:1213-1218IntroductionOccupational exposure to crystalline silica can be associated with either chronic or acute pulmonary disease. Chronic silicosis becomes manifest 20 to 40 years after first exposure and is characterized by development of concentric hyalinized nodular lesions in the lung with the de-velopment of dyspnea over a period of several decades. Acute silicosis, on the other hand, is manifested by a rapid on-set after exposure and is characterized by the accumulation of an amorphous granular lipoprotein exudate in the airspaces and rapid development of respiratory disability within a few years (1-3).Information is growing concerning the etiology of chronic silicosis. Studies sug-gest that several mechanisms may be in-volved in the development of fibrosis. Lung injury may result from silica-induced release of lysosomal enzymes from alveolar macrophages (4, 5). In ad-dition, silica-induced activation of su-peroxide anion and hydrogen peroxide release from alveolar macrophages may result in oxidant-induced damage to lung parenchyma (6). Silica exposure can also result in the release of mediators from alveolar macrophages which enhance the proliferation of fibroblasts and the syn-thesis of collagen by these pneumocytes (7, 8)."

Jan 1, 1988

By X. Shi, K. S. Kaspnak

"The generation of free radicals from reactions of nickel (Il)-thiol complexes with molecular oxygen and model lipid hydroperoxides was investigated by electron spin resonance (ESR) utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap. Incubation of nickel (II) [Ni(II)) with cysteine in an aerobic environment generated hydroxyl (·OH) radical, which then reacted with cysteine to generate a carbon-centered alkyl ( · R) radical. Radical generation was inhibited under a nitrogen atmosphere. Model lipid hydroperoxides, cumene hydroperoxide, and I-butyl hydroperoxide enhanced the yield of these radicals and also generated an alkoxyl (·OR) radical. Radical yield decreased by approximately half under a nitrogen atmosphere. Although histidine did not cause radical formation in the reaction between Ni(II) and cumene hydroperoxide under aerobic conditions, the addition of histidine to a mixture containing Ni(ll), cysteine, and cumene hydroperoxide under the same experimental conditions increased the yield of · R radical but lowered the yield of ·OR and ·OH radical adducts. It thus appears that histidine caused the ·OH attack to be more site-specific. Similar results were obtained utilizing 1-butyl hydroperoxide. Penicillamine or N-acetylcysteine yielded similar results except that under aerobic conditions, reaction between Ni(ll) and N-acetylcysteine without hydroperoxide did not generate a significant concentration of free radicals. Under the same experimental conditions, cystine did not generate any detectable free radicals, suggesting an important role of the -SH group in Ni(II)-mediated free radical generation. The results indicate that free radical generation from the reaction of Ni(Il)-thiol complexes and molecular oxygen, and/or lipid hydroperoxides, may play an important role in the mechanism(s) of Ni(II) toxicity and carcinogenesis. INTRODUCTIONWhile nickel is a well-recognized carcinogen [l, 2]. the underlying biochemical mechanisms remain unclear (3, 4). Recent studies suggest that these mechanisms may involve oxidative DNA damage through free radicals, especially the hydroxyl (•OH) radical [5-13]. The mechanisms of nickel carcinogenicity and toxicity may also involve lipid peroxidation [14-21]. Unlike ferrous ion [Fe(II)], the Ni(II) cation itself does not directly react with 02, H2O2, or lipid hydroperoxides to generate free radicals [12, 21]. However, it has been reported that Ni(II) complexes with certain synthetic oligopeptides, e.g., tetraglycine or glycylglycylhistidine, make Ni(II) reactive with 02. This reaction results in transitory formation of Ni(III) and degradation of the organic ligand via free radical reactions [22]. Such Ni(II)-peptide complexes are also capable of reacting with H2O2 to produce oxygen free radicals [11, 12]. Although the cellular environ¬ment may not contain these particular peptide ligands that are known to render Ni(II) redox active in vitro, it does contain a variety of oligopeptides that are capable of forming Ni(II) complexes at physiological pH, and thus may facilitate Ni(II) redox activity in vivo. These oligopeptides include glutathione (y-L glutamylycysteinylglycine), carnosine (homocarnosine (y aminobutyryl-L-histidine), and anserine ( B-alany1-3-methyl-L-histidine)."

Nov 1, 1995