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By E. G. King

The literature contains little thermodynamic information regarding inter-oxidic compounds of the ferroalloy elements and, as a result, thermodynamic considerations of extractive and utilization processes involving these elements have been hampered. As part of a Bureau of Mines program to improve this situation, this paper reports the heats of formation of three calcium vanadates and two magnesium vanadates. There were no previous similar data for any of these compounds. The experimental method was hydrochloric acid solution calorimetry, using calorimetric reaction schemes involving the vanadates and their component oxides. The results were expressed as heats of formation from the component oxides and from the elements. Corresponding free energy of formation values were calculated. The data show that the calcium and magnesium vanadates are stable with respect to all possible decompositions in which vanadium remains pentavalent. This conclusion is similar to the one drawn by Koehler6 for three sodium vanadates.

Jan 1, 1962

By J. A. Cavallaro

The heats of formation of anhydrous barium carbonate (witherite), strontium carbonate (strontianite), and lead carbonate (cerussite) were determined by solution calorimetry. The solution mediums were hydrochloric acid for barium and strontium carbonates and perchloric acid for lead carbonate. The heats of formation at 298.15° K are as follows: BaCO3 -297.5 ± 0.8 kcal/mole; SrCO3 -294.6 ± 0.5 kcal/mole; and PbCO3 -168.0 ± 0.3 kcal/mole.

Jan 1, 1966

By William K. Cunningham

The investigation described in this report was begun as part of the Bureau of Mines progress to develop acid processes for the extraction of alumina from low-grade bauxite and. clays. A domestic shortage of high-grade bauxite sui table for treatment by the Bayer process became acute as a result of' World War II; an intensive search for a practical acid process using lower-grade alumina-bearing raw materials was therefore warranted. The laboratory development was described in a preceding Bureau of Mines publication wherein the basic theory for the design and erection of a pilot plant maybe found. A 2-ton-per-day continuous pilot plant was constructed and successfully operated at College Park, Md., which demonstrated conclusively the chemical and mechanical feasibility of a solvent purification process for aluminum sulfate. The estimated production cost of $38.64 indicates that under present market conditions the process would not be economically feasible.

Jan 1, 1948

By R. Barany

The heats of formation at 298.15° K of calcium tungstate, calcium molybdate, and magnesium molybdate were determined by solution calorimetry. For the heats of formation from the elements, the values obtained were calcium tungstate, -402.4 ± 0.5 kcal/mole, calcium molybdate, -369.5 ± 0.3 kcal/mole, -334.8 ± 0.2 kcal/mole. For the heats of formation from the oxides J the values obtained were calcium tungstate, -49.2 ± 0.4 kcal/mole, calcium molybdate, -39.6 ± 0.1 kcal/mole, and magnesium molybdate, -12.9 [ ] 0.1 kcal/mole.

Jan 1, 1962

By N. S. Dalal, B. Jafari, F. Y. H. Green, V. Vallyathan

"Using electron spin resonance (ESR) spectroscopy we have carried out a systematic study of the measurement of concentrations of organic free radicals in freeze-dried lung tissue. Sixty-six tissue samples were obtained from the National Coal Workers' Autopsy Study (NCWAS). The samples were characterized in terms of the concentration per gram of the free radicals, and examined in relationship to the histopathological parameters such as age, numbers of years in the mining atmosphere, the degree of disease, and smoking history. Preliminary results indicate a positive correlation between the free radicals in the lung tissue and the severity of pneumoconiosis.IntroductionThis paper summarizes our electron spin resonance (ESR) measurements of the concentration of organic free radicals in the freeze-dried lung tissue of autopsied coal miners. This work was undertaken because it is well known that most coals contain carbon-centered organic free radi¬cals,(1,2) and recent studies from our laboratories indicated that reactive free radicals might play a role in the biochemi¬cal mechanism of coal workers' pneumoconiosis (CWP) (3) Thus we obtained 144 lung-tissue samples from the Nation¬al Institute for Occupational Safety and Health (NIOSH) in Morgantown. The samples came from the data bank of the National Coal Workers' Autopsy Study (NCWAS). This selection was unique because fairly detailed histopathologi¬cal information was available for each sample.Other recent studies in this field are those of Ohta et al (4) who conducted ESR measurements on black dust deposited in autopsied human lungs, but no coal miner was included therein. Earlier Retcofsky (2) had examined one lung-tissue sample via ESR spectroscopy and had concluded that the free radicals in the lung tissue reflected simply the fusain (narrow component) ESR signals. The present study was thus undertaken to complement the earlier work (2-4) and the results indicate a positive correlation with the disease severity fairly strongly."

Mar 1, 1989

By R. Barany

Thermodynamic calculations pertaining to the minerals gibbsite, kaolinite, halloysite, and dickite have been hampered by the lack of adequate heat and free energy of formation data. Previous data for gibbsite were highly uncertain, and there were no data for the other three substances. By use of hydrofluoric acid solution calorimetry, the Bureau of Mines derived heat of formation values from the elements and from the oxides for the four substances, and the data were combined with known entropy values to obtain the corresponding free energies of formation. The results show that gibbsite and halloysite are thermodynamically unstable with respect to the oxides (a- alumina, a- quartz, and liquid water) at 298.15° K,, while kaolinite and dickite are only moderately stable (to about the same degree), The instability of halloysite, in comparison with kaolinite and dickite, results in a 60°-lower equilibrium decomposition temperature.

Jan 1, 1961

By W. H. Ode, W. A. Selvig

In 1938 , the Bureau of Mines cooperated with Subcommittee XV on Plasticity and Swelling of Coal ( C. C. Russell , chairman ) , of Committee D-5 on Coal and Coke , A.S.T.M. , by testing various methods for determining expansion and plastic properties of a series of coals of widely different coking properties . One of the tests made by the Bureau was the British Standard Method for the Crucible Swelling Test for Coal.5/ Briefly , this swelling test consists in heating 1 gram of pulverized coal in a silica crucible over a gas flame under prescribed conditions to form a coke button which is compared in size and shape with a series of standard profiles numbered 1 to 9. These profiles are intended to cover the size and shape of buttons obtained from coals covering a wide range in plastic properties .. The number of the standard profile with which the maximum cross -sectional area of the button most nearly corresponds is recorded as the swelling index . Although the swelling test showed poor relationships with the various tests that were used for measuring expansion or contraction of coal during carbonization , it gave indications of having value in measuring free - swelling and caking properties of coals when burned on fuel beds . An opportunity to investigate this occurred when an engineer of an eastern public utility 'company reported pronounced differences in burning characteristics on grates of various shipments of Pocahontas coal . Some of these coals gave trouble by swelling 'excessively and clogging the grates . Samples were ob- · tained , and it was found that the troublesome coals gave decidedly higher free -swelling numbers than did the coals that performed satisfactorily . Also , it was found that the free - swelling index test gave better differentiation between coals than could be obtained from the coke buttons from the · ´`standard volatile -matter test or from agglutinating - value results . The results of the free - swelling tests were considered by the Subcommittee on Plasticity and Swelling , and a special group of the subcommittee , under the chairmanship of R. A. Sherman , was delegated to study the test method . Ostborg , Limbacher , and Sherman , ofthe Battelle Memorial Institute , ' investigated the various factors affecting the test and found that the swelling index was a good indication of the suitability of coal for performance on residential -type stokers from the standpoint of the coking characteristics of the coal . Data were presented also showing that the indexes wer helpful in the selection of coal for industrial underfeed stokers .

Oct 1, 1946

By F. A. Penning

A number of highly instrumented free fall tests were performed on an arrestment system for a man cage in a vertical shaft. Tests were conducted in the U.S. Bureau of Mines free fall test tower at the Colorado School of Mines. A single tooth safety dog was used to stop on 4x6-in. Keruing (Phillipine mahogany) wet and dry wood guides. The safety dog had a penetration depth of 1 in., an adjustable width from 1-1/2 to 2-1/4 in., and a tooth angle of 80 deg. Twenty-seven free fall tests were performed covering a range in weights from 3-1/2 to 10-1/2 tons, hoisting velocities from 850 to 1350 feet per minute. Average g loads were measured from a low of 0.6 to a high of 3.4. The electronic instrumentation included piezoelectric and seismic mass accelerometers, strain gages on structural and mechanical elements, load cells in the guides, and distance measuring. Computer analysis was used to correlate with experimental measurements used to calculate stress. A statistical analysis gave no indication that the velocity or area affected the wood crushing stress. The instrumentation revealed a chatter occurring during the stop as shown by the accelerometers, strain gages, and load cells. Additional work is required to analyze this newly discovered phenomenon. The chatter imposes loads much higher than the average g load.

Jan 1, 1980

By Alla D. Mah

The heat of formation of scandium sesquioxide (Sc203) has not been measured previously, and existing values for gallium sesquioxide (Ga203) are subject to large uncertainties. As a consequence, thermodynamic calculations involving these oxides hare lacked scientific exactness. This paper reports newly determined values of the heats of formation of gallium and scandium sesquioxides at 298.15° K., by combustion calorimetry. The corresponding free energies of formation are derived from heat and entropy data.

Jan 1, 1962

By A. C. Fieldner

[The Sectional Committee on Classification of Coals, functioning under the sponsorship of the American Society for Testing Materials and the rules of the American Standards Association, in its 1934 report recommended to the American Society for Testing-Materials that Specifications for Classification of Coals by Rank be adopted as tentative. These specifications, slightly modified as recommended by the Sectional Committee, in its 1935 report,6 wore approved as tentative standards by the society in 1935. The specifications rover the classification of coals according; to their degree of metamorphism, or progressive alteration, in the natural eerie s from lignite to anthracite. The basic scheme of classification is according to fired carbon and calorific value (expressed in B.t.u.) calculated to the mineral-matter-free basis. The higher-rank coals are classified according to fixed carbon on the dry basis, and the lower-rank coals according to B.t.u. on the moist basis, that is, containing its natural bed moisture but free of visible surface moisture. Agglutinating and weathering indices arc used to differentiate between certain adjacent groups.]

Jan 1, 1935

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 Seth C. Schaefer

The Federal Bureau of Mines studied the Gibbs free energies of formation of chromous fluoride (CrF2), chromic fluoride (CrF3), and chromium (II,III) fluorides (CrF2.40 and CrF2.45) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pct yttrium fluoride as the electrolyte. Free-energy changes were obtained from open-circuit potential measurements for the following cells: Cr, CrF2 // CaF2 // NiF2, Ni (a) NiO, NiF2 // CaF2 // CrF3 , Cr203 (b) CrF2 , CrF2.40 // CaF2 // NiF2, Ni (c) and CrF2 ?45 , CrF3 // CaF2 // NiF2, Ni (d) with the following overall reactions Cr(s) + NiF2 (s) = Ni(s) + CrF2 (s) (1) 3NiO(s) + 2CrF3 (s) = 3NiF2 (s) + Cr203 (s) (2) 5CrF2 (s) + NiF2 (s) = 5CrF2.4O (s) + Ni(s) (3) and 3.64CrF2.45 + NiF2 (s) = 3.64CrF3 (s) + Ni (s) . (4) These results were combined with the best available literature values of ?Gf° of NiF2, NiO, and Cr203 to deduce Gibbs free energies of formation for the chromium fluorides expressed as follows: ?Gf°(CrF2) = -179.31 + 24.33 X 10-3T ± 0.43 kcal-mole. (5) (858.1 - 964.9 K) ?Gf° (CrF3) _ -226.16 + 1.82 X 10-3T ± 0.79 kcal/mole (6) (880.8 - 957.8 K) ?Gf°(CrF2.40) _ -213.65 + 32.14 X 10-3T ± 0.44 kcal/mole (7) (0053.9 - 936.8 K) and ?Gf°(CrF2.45) _ -176.17 - 12.67 X 10-3T ± 0.80 kcal/mole (8) (875.1 - 937.6 K). Free energies and equilibrium fluorine pressures for three univariant and one bivariant equilibria are illustrated.

Jan 1, 1976

By X. Shi, V. Vallyathan, N. S. Dalai

"Using. ESR spin trapping methodology, evidence was obtained that fresh quartz dust in a cell-free aqueous medium generated hydroxyl - and possibly superoxide radicals. The hydroxyl radical generation potential decreases on storing of fresh quartz dust in ambient air and on the addition of either catalase, superoxide dismutase, desferoxamine, or DMSO. The role of quartz related radicals in the biochemical mechanism of acute silicosis is suggested from these findings.IntroductionThis report summarizes our electron spin resonance (ESR) detection of oxygenated radical formation by freshly crushed quartz particles in a cell-free aqueous medium, and its inihibition by radical scavengers. This study was undertaken with to elucidate the primary biochemical mechanism involved in the development of silicosis (Farber, 1983; Reiser and Last, 1979; Silicosis and Silicate Disease Committee, 1988). In particular the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still not well understood (Farber. 1983; Reiser and Last, 1979;). It is generally believed that the action of quartz particles on the cell membrane is the starting point of the silicotic process (Farber, 1983; Parazzi et al., 1968). Thus the surface characteristics of the quartz particles have been the subject of several recent studies (Bolls et al.. 1983; Dalai et al., 1986; Fubini et al., 1987). Recently, We reported that mechanical crushing of quartz under normal atmosphere generates free radicals which decay with time, and that these free radicals are associated with a higher cytotoxicity of fresh quartz dust as compared to aged dust from the same stock (Dalai et al., 1986; Vallyathan et al.. 1988). The formation of Si• and. SiO--type of radicals from quartz particles crushed under atmospheric conditions has also been reported by Fubini et al. (1987). In addition, Gulumian and van Wyk (1987) have reported that quartz particles react with hydrogen peroxide (H202) to generates hydroxyl radicals (•OH) and suggested that this process might contribute to quartz's pathogenicity. However, these authors did not report the effects of metal chelators, so it was not clear as to whether the detected -OH radicals simply resulted from the Fenton reaction involving exogenous metal ion contaminants. Earlier, Marasas and Harington (1960) reported that quartz particles could function as an oxidant in a number of in vitro oxidations, including the hydroxylation of proline and lysine. They postulated that silica dusts, on reacting with water, could release H2O2 which might have the potential to react with various biological constituents and thus cause tissue damage. In fact, Gabor and coworkers (Gabor and Anca, 1974; Gabor et al., 1975) suggested that the cytotoxicity of quartz particles might be associated with the generation of some 'factor or factors possessing the properties of a free radicals capable of promoting the peroxidative chain cleavage of polyunsaturated fatty acid moieties of the phospholipids in the cell membrane. More recently Weitzman and Graceffa (1984) reported that asbestos is able to catalyze the generation of • OH radicals from H2O2. Their later work indicated that lipid peroxidation may be one of the mechanism by which asbestos produces tissue injury (Weitzman and Weitberg, 1985). This is significant because • OH radicals are capable of causing peroxidation by abstracting hydrogen atoms from cell-membrane lipids and initiating lipid peroxidation in lysosomal membrane (Fong et al., 1973). In fact, the formation of oxygenated species in reactions involving quartz was suspected since Kolbanev et al. (1980) reported the detection of H2O2 in the reaction of fresh quartz particle with aqueous medium. The present work was thus undertaken to detect the anticipated formation of some oxygenated, radical species by reactions of quartz in a cell-free media and its inhibition by radical"

Jan 1, 1988

By R. Barany

This paper reports determinations of heats of formation (from the oxides and elements) of crystalline cadmium metasilicate and crystalline lead meta-silicate by hydrofluoric acid solution calorimetry. The results, in conjunction with known entropy values, yield free energies of formation. There are no earlier data of this type for cadmium metasilicate. The results of this investigation for lead metasilicate deviate from the literature values (which are less reliable) in the direction of increased thermodynamic stability. Both cadmium and lead metasilicate are much less thermodynamically stable with respect to their constituent oxides than are the corresponding compounds of the alkaline earth metals.

Jan 1, 1959

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

By K. K. Kelley

Despite the wide interest in titanium and its compounds, no heat and free-energy-of-formation values for titanates (that is, compounds formed from titania and other metal oxides) have been available heretofore except for ilmenite (FeTi03). Such data are needed for understanding and developing processes for producing titania and titanium tetrachloride from ores (and possibly slags) and in connection with ceramic usage of titania. This paper reports experimental measurements of the heats of formation at ordinary temperature of 11 titanates-ilmenite, perovskite, barium metatinate, strontium metatitanate, barium-strontium metatitanate, barium orthotitanate, strontium orthotitanate, barium-strontium othotitanate, geikielite, magnesium-titanium spinel, and magnesium dititanate. The experimental method was solution calorimetry. The solution calorimeter was operated at 73.7°C. and used a strong hydrofluoric-hydrochloric acid mixture as the calorimetric fluid and reaction medium.

Jan 1, 1954

By M. Hertzberg

This Bureau of Mines report describes experimental and theoretical studies of diffusion flames in free convection. The cross-coupling between buoyancy-induced flows and the combustion process is explored as it relates to the size, structure, and radiative balance of flames. New data are presented for the size-dependent radiance oscillations of diffusion flames and for the angular distribution of the total radiant intensity from a small methanol pool flame. Both amplitude and frequency of the measured oscillations are compared with theoretical predictions that are based on a new view of the structure of diffusion flames. This new view, which is at variance with the traditional one, assumes uniform reaction in the diffusive mixing zone, and recognizes the significance of the role played by convective buoyancy and its duality in both aiding and impeding flame propagation. Buoyancy quenches propagation at low burning velocities, introducing a real discontinuity in the combustion rate. A "flammable volume" is thus defined as that bound between lean- and rich-limit contours. However, in the flow disturbances generated by combustion waves that consume that volume, buoyancy aids propagation by promoting the convective mixing of a new flammable volume. The measured radiance oscillations are manifestations of these propagation and remixing cycles.

Jan 1, 1978

By O. C. Baptist

The gravitational pressure gradient (GPG) in porous sandstone containing free gas was determined to define the proper GPG to use when calculating the rate of downdip flow of oil in the Sub-Scalez No, 1 sand, Elk Hills field, Naval Petroleum Reserve 1. The GPG was determined at several gas saturations using long, artificially consolidated sandstone models that were mounted vertically in some tests and horizontally, with rotation, in others. Also determined by laboratory and field tests were relative permeabilities, capillary pressure relations; critical gas saturation, water sensitivity, and depletion drive performance. The critical gas saturation in the models having an absolute permeability of 1 to 2 darcys was about 2 percent of pore volume. The GPG with the critcal gas saturation was that due to the weight of the gas-saturated oil. The GPG in the upper part of the models was reduced as gas saturation increased to a value considerably larger than the critical. The exact gas saturation at which the GPG became less than that due to the weight of the oil could not be determined but was estimated to be of the order of 10 percent of pore volume. Tests indicate that the rate of oil production is not permanently reduced by exposure of the sand to fresh water but that the rate of injection of fresh water will be considerably less than that to brine, Methods for determining the factors mentioned above are discussed.

Jan 1, 1967

By Nar S. Dala1, Xianglin Shi, Val Vallyathan

"Electron spin resonance (ESRJ and cytotoxicity measurements were made on newly fractured silica to examine specifically the role of the fracture-induced, silicon-based radicals (Si· and SiO·) and silica-generated hydroxyl (·OH) radicals in the mechanism of the cell membrane damage by silica. The concentration of the Si· and SiO · radicals was controlled through decay processes, thermal annealing, and boiling, while that of the ·OH radicals was varied by using catalase, superoxide dismutase, KMnO, Na;iSeO:y ascorbic acid, and metal ions, and monitored via ESR spectroscopy. The dust's cytotoxicity potential was evaluated by measuring the silica-induced hemolysis and also by determining lipid peroxidation (using linoleic acid). From the comparison of hemolysis and ESR results it is deduced that the radicals play little or no role in the silica-induced hemolysis. However, the lipid peroxidation data indicate that the radicals might be involved in the initiation of an oxidative chain reaction leading to the macrophage membrane damage through lipid peroxidation. INTRODUCTIONThe biochemical mechanism of quartz-related pneumoconiosis is still not fully understood. It is believed, nevertheless, that one event of primary importance is the perturbation of cell membranes by the dust particles (Allison et al., 1966; Allison and Harrow, 1971; Bateman et al., 1982; Parazzi et al., 1968; Reiser and Last, 1979; Shi et al., 1989; Summerton et al., 1977). The ensuing cell: membrane damage unleashes certain lytic enzymes resulting in additional cell injury and eventual fibrosis (Nolan et al., 1981; Summerton et al., 1977). Thus considerable effort is currently being made toward the understanding of the processes by which quartz particles disrupt the membrane of a red blood cell (RBC) or a pulmonary alveolar macrophage (PAM). A simple but important method of evaluating the membrane damage potential of a dust is the hemolysis test (Harington et al., 1971). Even though this test is used routinely for screening dusts for their cytotoxicity potential, the biochemical mechanisms underlying the cell lysis by many dusts, including quartz, is still controversial (Kilroe-Smith, 1974; Singh and Rahman, 1987), and this provided us the impetus for the present undertaking."

Jan 1, 1990

By C. Ortuglio

The effect of cracking by increasing the free space above the charge on the composition and yields of the volatile products from carbonization of Pittsburgh-bed coal and one industrially used blend from Eastern United States and one from Western United States was investigated with the BM-AGA carbonization apparatus. Increasing the free space above the charge from 1 inch to 3 inches, to 6 inches, and to 9 inches resulted in lower tar yields and increased gas and light oil yields. Anthracene and naphthalene yields were increased; quinoline and benzene insoluble fractions of both the tar and pitch increased considerably with increased free space, although the carbon content of the tars and pitches increased only slightly. Increased cracking, occasioned by the increase in free space, resulted in a decrease in the yields of tar acids, tar bases, neutral oils, olefins, aromatics, and paraffins and naphthenes. Gas composition was relatively constant; hydrogen and methane tended to increase and ethane decrease. Results of the investigation are being used to design a unit to upgrade the volatile products of carbonization by cracking the hot products as they leave the carbonization chamber.

Jan 1, 1970