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By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By C. A. Holley

Agitative agglomeration is a rapidly expanding field related to many chemical processes. This paper reviews many processes and the particular type of agitative agglomeration that is utilized with each. Many new innovations to produce granular products in place of powder are explored. The operation and theory of the many types of agitative agglomeration equipment is reviewed.

Jan 1, 1988

By David A. Lipton

In the summer of 1985, at the request of the U.S. Forest Service, the U.5. Bureau of Mines examined the 109,000-acre West Big Hole study area to evaluate its identified mineral resources. The study area is in Beaverhead County, about 50 mi west of Dillon, MT. Four lode properties within or adjacent to the study area contain an estimated 452,000 tons of identified subeconomic gold-silver resources. Resources ranged from 900 to 302,000 tons, with estimated grades between 0.02 and 0.23 oz/ton gold and as much as 4.8 oz/ton silver. Gold, silver, and base-metal content in samples of poorly exposed mineralized structures indicate that exploration may identify resources on 18 additional lode properties within the study area and 5 properties adjacent to it.

Jan 1, 1988

By M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

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

"Electron spin resonance (ESRJ spectrum of the hydroxyl (· OH) radical spin adduct with .the spin trap 5,5-dimethyl-1-pyrrolintt-N-oxide has been obtained in suspensions of freshly ground quartz particles. The concentration of the spin adduct (and hence of the • OH radicals) increases with the amount of grinding. The dust's potential for the generation of the· OH radicals is maximum when fresh (i.e., immediately after grinding) and decreases to 50% in about a day on storage in air. Studies involving metal chelates .indicate that the • OH radical formation involves mainly the silica surface and H20 rather than the Fenton reaction. The results suggest that hydroxyl radical reaction(s) could be important in the lipid peroxidation and fibrogenicity by quartz dust, particularly .in acute silicosis. INTRODUCTIONIn this paper we report on our electron spin resonance (ESR) detection of the formation of hydroxyl (·OH) radicals in aqueous suspensions of freshly crushed quartz particles. This work was undertaken with a view to find possible clues to the role of free radicals in the pathogenesis of quartz-induced fibrogenicity, commonly known as silicosis. We noted that while silicosis is one of the major health hazards in coal and mineral industries, 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 poorly ·understood (Reiser and Last, 1979; Singh and .Rahman, 1987). It is generally thought, nevertheless, that the action of quartz particles on the biological membranes is the starting point of the silicotic process (Parazzi et - al., 1968). A possible clue to the mechanism of the membrane damage by quartz particles, in terms of the role of oxygenated free radicals, is suggested by the following observations. A suspension of quartz particles in contact with alveolar macrophages has been reported (Gabor et al., 1975; Koike et al., 1982) to initiate an enhancement of lipid peroxidation, defined broadly as the oxidative deterioration of polyunsaturated components of lipids. Hydroxyl (· OH) radicals are known to be capable of peroxidation by abstracting hydrogen atoms from cell-membrane lipids (Halliwell and Gutteridge, 1985) and of initiating lipid peroxidation in lysosomal membranes. (Fong et al., 1973). Arong other lines, it is known that exposure of cell membranes, fatty acids, and unsaturated food oils to ionizing radiation, which generates· OH radicals, causes rapid peroxidation (Halliwell and Gutteridge, 1985). Thus • OH radicals (and also other oxygenated species such as Oi, 10 2, and H20 2) might be expected to play a role in the toxicity of quartz. Earlier studies of the aqueous chemistry of quartz suspensions have reported detection of H2O 2 (Kalbanev et al., 1980), implicating the formation of ·OH radicals as transient species. However, we are not aware of any report of the detection of • OH radicals in quartz reactions, and thus the present study was undertaken. Since it-is known that, because of their high reactivity (hence short lifetime) in aqueous media, the • OH radicals cannot be detected via ESR directly (Finkelstein et al., 1980; Buettner, 1982) we have used .ESR combined with the spin-trap methodology (Finkelstein et al., 1980) for studying the· OH formation. The results show that· OH radicals are indeed formed in aqueous suspensions of freshly ground quartz; thus pointing to ·a possible new clue to the cytotoxicity of freshly formed quartz particles and thereby to silica fibrogenicity."

Jan 1, 1988

By Paul W. Jeran

Subsidence over a series of longwall panels undermining sloping terrain in southwestern Pennsylvania was monitored to verify the Bureau of Mines subsidence prediction model for the northern Appalachian coal region. Comparison of the field data to model output shows close agreement. Vertical movements over each panel ceased with the mining of the adjacent panel. Horizontal movements were significantly affected by topographic slope. The distribution of horizontal strains over each panel were similar, with a zone of compression occurring over the center of each panel. The zones of compression were flanked by zones of tension toward the rib. The magnitude of the tensions were affected by the slope. The strains developed at the completion of each panel were not significantly altered by the mining of subsequent panels.

Jan 1, 1988

By S. A. N. Sheya

Many gold-bearing ores in the Western United States also contain small amounts of mercury. The presence of mercury creates potential pollution and health hazards during several steps in gold processing. An investigation was undertaken by the Bureau of Mines to develop techniques for removing mercury from cyanide mill solutions by selective electrowinning to reduce the potential hazards. Sixty-five percent of the mercury was selectively electrowon from synthetic carbon strip solution at applied potentials of 1.00 to 1.50 V when using a mercury-coated platinum or copper plate cathode. Increasing the active surface area by using mercury-coated copper wool resulted in up to % pct of the mercury being electrowon from mill carbon strip solutions that contained 1.9 to 20 ppm Hg, 20 to 345 ppm Au, and 0.35 to 39.5 ppm Ag. About 98 pct of the silver was electrowon with the mercury onto the mercury cathode. Gold extraction ranged between 0 and 20 pet. Results of the investigation showed that choice of cathode material was critical to the success of the process. Selectivity was not achieved using uncoated steel wool cathodes.

Jan 1, 1988

By T. Langthaler, H. W. Engl, H. Holl, K. L. Schwaha

"The trend towards near net shape casting requires the development of more complex design and control algorithms for continuous casting ""machines in particular with respect to the solidification process.Compared to conventional continuous casting the reduction in casting thickness allows to influence more directly the solidification rate by control variables like surface cooling and/or casting speed.In order to enable the determination of these control variables for a given solidification profile, an algorithm (inverse solidification analysis) has been developed based on nonlinear constrained optimization. The application of the model is illustrated by practical examples ranging from conventional continuous casting to advanced thin slab casting.IntroductionProcess development in the Iron and Steel Industry is directed towards the realization of continuous process sequences. Since the direct linkage of processes imposes some restrictions onto the individual process steps, more complex algorithms are needed for design of equipment and control of operation. In particular the recent trend to reduce casting thickness, i.e. to cast thin slabs, has made the direct coupling of continuous casting and rolling absolutely necessary. The prospective development in strip production is schematically shown in fig. 1."

Jan 1, 1988

By Eugene V. Cilento, R. Clark Lantz, Kevin A. DiGregorio

"A microscope-based spectrophotometer has been developed to measure superoxide release from single pulmonary alveolar macrophages (PAM) or other phagocytes in culture. Results indicate that PAM respond to stimulation by phorbol myristate acetate (PMA). It appears that some PAM do not release 02 upon stimulation by PMA; however, those that do release 0, show differences in: (I) the total amount of 0, released, (2) the rate of release of 02 and (3) the time delay for release of 02. The significance of measuring 02 release from single cells is two-fold. It allows the simultaneous study of 02 release and electrical potential changes across the membrane of PAM and it allows the study of differences in 02 release among cells. Thus, the function of Normal PAM and the dysfunction of PAM exposed to coal dusts can be more closely studied on single cells.Pulmonary alveolar macrophages (PAM), free cells found in the lungs, protect the lungs by removing inhaled foreign debris and bacteria. The macrophages do this by engulfing and then internalizing the foreign matter (phagocytosis). Stimulation of PAM causes the release of super-oxide radical (02) which has been shown to be the primary metabolite involved in the killing of bacteria by phagocytes (3,8,12). The super-oxide radical is highly reactive and is spontaneously or enzymatically converted to other antibacterial oxidants, including hydrogen peroxide (H202), singlette oxygen ( 02), hydroxyl radical toil'), and hypochlorous acid (HOCl) (2, 3,8,11,12).Exposure of PAM to dusts may lead to dysfunction of this cell-type and to a greater risk of lung damage or infection upon subsequent exposure to toxic dusts. To date, much of the research with this cell-type has used cytotoxicity (cell death) as a measure of dysfunction. Although this is an important end point, PAM dysfunction may occur at doses below those which lead to cell death. In addition, dysfunction has been measured using large numbers of cells. In order to obtain a clear understanding of the mechanisms involved in dysfunction, measurements should be made on single cells. As mentioned earlier, one of the major roles of this cell type is its anti-bacterial actions. Therefore, asessment of release of superoxide radical in single cells is important in determining the functional behavior of PAM before and after exposure to dusts. Since measurements of 02 production have not been made on single cells the purpose of this study is to develop the methodology needed to study release of 02 from single cells.Recent studies have suggested that a relationship exists between the release of 02 and changes in the electrical properties of phagocytes. The change in membrane potential is thought to be the initial step in superoxide production (6,9). Stimulants which cause 02 release also cause changes in the transmembrane potential of phagocytes (9) and in the permeability of the cell membrane to ions (6). For example, stimulants which cause the release of 0, from neutrophils have also been shown to increase the membrane transport of Na+ , K+ and Ca+2 and stimulation of macrophages leads to increases in Na and perhaps Ca permeability with a subsequent change in membrane potential. In some cases, phagocytic activity has been shown to depend upon the extracellular concentrations of these ions (6). Holian and Daniele (7) have shown evidence that the redistribution ofcellular Ca in alveolar macrophages is an initial step leading to 0, release. In order to provide direct evidence that 02- production is related to electrical changes across the plasma membrane of phagocytes, these two phenomena must be analyzed simultaneously on single cells. Ultimately, measurements of 0, release using the methodology developed in this study will be combined with electrophysiological tech¬niques to study both superoxide release and membrane potential changes simultaneiously on single PAM, and to examine the effects of coal and mineral dusts on their physiological fu"

Jan 1, 1988

By Michael S. Miller

In 1986 and 1987, at the request of the U.S. Bureau of Land Management, the U.S. Bureau of Mines studied the nine separate parcels that comprise the 4,330-acre South Warner Contiguous Wilderness Study Area in order to evaluate their identified mineral resources. The nine parcels are along the east side of the South Warner Wilderness. They are, from north to south, the Granger, Milk, Cottonwood, Owl, Hornback, Eagle, Emerson, Barber, and Van Riper parcels. The Wilderness Study Area is underlain by basaltic, andesitic, and rhyolitic volcanic rocks and by sand and gravel deposits. Low-grade metamorphism is widespread in the volcanic rocks, with quartz, zeolites, datolite, chlorite, and calcite locally abundant in veins and amygdules. The rocks have been displaced by the mountain-front Surprise Valley fault and by crosscutting high-angle faults.

Jan 1, 1988

By E. G. Noble

The effects of HBr concentration and temperature on the solubility and hydration state of AlBr3,' CoBr2, PbBr2, MnBr2, KBr, and NaBr were investigated by the Bureau of Mines. Saturated aqueous solutions of the AI, Pb, K, and Na bromides were sparged with HBr gas at 20°, 40°, and 60° C, and saturated solutions of Co and Mn bromides were sparged at 20° C. Increased HBr concentration caused decreased salt solubility because of the common ion effect for all the investigated bromides except PbBr2. Aqueous solubilities at 20° C were, in percent, 51.7 for AlBr3, 53.2 for CoBr2, 1.1 for PbBr2, 59.6 for MnBr2' 39.5 for KBr, and 47.4 for NaBr. At 60° C, the solubilities were, in percent, 53.3 for AlBr3, 2.2 for PbBr2' 46.0 for KBr, and 53.8 for NaBr. Solubilities in solutions sparged to HBr saturation at 20° C were, in percent, 0.5 for AlBr3, 42.0 for CoBr2, 32.2 for PbBr2, 21.0 for MnBr2, 0.6 for KBr, and 0.3 for NaBr. At 60° C, the solubilities at HBr saturation were, in percent, 1.8 for AlBr3, 41.4 for PbBr2, 1.3 for KBr, and 0.4 for NaBr. CoBr2 precipitated out to a minimum solubility of 27.2 pct at 28.7-pct-HBr concentration. Further increases in HBr concentration increased CoBr2 solubility because of the formation of bromide complexes. PbBr2 in-creased in solubility as HBr concentration increased.

Jan 1, 1988

Humic acids adsorb on coal and depress coal floatability in the acidic pH range. In alkaline solutions, their effect is not pronounced. In the neutral pH range, a second small addition of kerosene plus MIBC leads to a significant increase in coal yield and better selectivity. Humic acids present on oxidized coal surface were found to be responsible for the inhibited floatability of the? coal. As expected, the flotation of such oxidized coal also strongly depends on the method of pH adjustment.

Jan 1, 1988

By Thomas M. Barczak

The effect of load rate on the load-carrying capabilities of wood cribs is investigated in this Bureau of Mines study. The modulus of deformation (stiffness) of wood crib blocks has been shown to increase with increases in rates of load application, causing larger load reactions for increases in convergence rates. Since wood cribs are tested in the laboratory at convergence rates that are orders of magnitude faster than typically would occur underground, wood cribs tested in the laboratory will react larger loads than the same cribs would react underground for the same displacement. Tests conducted in the Bureau's mine roof simulator on green wood crib blocks indicate that the increase in stiffness for increasing load rates diminishes at displacement rates beyond 0.1 in/min, making crib load nearly independent of load rate for rates faster than 0.1 in/min. Seasoned wood specimens were not as con-sistent in load-rate dependency. Some possible explanations of observed load-rate behavior on wood crib specimens are also postulated in this paper.

Jan 1, 1988

By Joan Weinberg

Real gross national product (GNP) grew at a seasonally adjusted annual rate of 2.2% in the third quarter, down from a revised 3.0% in the second quarter, according to preliminary data from the U.S. Department of Commerce (table 1). The slowdown in the rate of growth was attributed to the summer drought, a larger trade deficit, and a decline in Federal spending for defense. Exports slowed from the second quarter, as the dollar, compared with other industrial country currencies, edged up. Imports of both consumer goods and capital goods rose sharply, with consumers buying more foreign cars, computers, and electrical machinery. Although net exports of goods and services deteriorated slightly from the second quarter, the U.S. trade position continues to be much improved from 1987 and first quarter, 1988. Business spending for new plant and equipment rose at a 4.6% pace, well below that recorded earlier in the year. The 3.5% increase in consumer expenditure was accounted for mainly by nondurable goods and services; expenditure for durable goods--those products lasting more than 3 years--rose only 0.4%. Inflation, as measured by the fixed-weighted GNP price index, rose at an annual rate of 4.9% in the third quarter. Prices rose slightly less than they had in the second quarter, when inflation reached a 6-year high. In September, 1988, the President signed a U.S.-Canada free trade agreement (FTA) which will eliminate all tariffs and most nontariff barriers between the two countries by 1999, thereby creating the world's largest open market. In 1987, U.S.-Canadian bilateral trade totaled $161 billion. The expansion of trade is expected to generate 5% higher growth for Canada and up to 1 % higher growth for the United States by the end of the century. The higher growth for the United States translates into an estimated 750,000 jobs, and $2.4 billion in exports. Canadian parliamentary approval of the agreement is still required before the treaty can take effect. The debate in Parliament is continuing, and the issue is not expected to be resolved until after the November 21 election.

Jan 1, 1988

By I. H. Clark

In some mining situations, backfills are not only required to be free-standing but are also expected to provide hangingwall support. It may therefore be specified that the backfill withstand a certain calculated stress within a given time. Given the materials available, the choice of backfill composition is not always straightforward, and an approach to the evaluation of cemented tailings backfill is therefore proposed. The general use of such a method will greatly assist in both the scientific analysis of the material properties for industry-wide purposes of comparison and decision-making as regards the choice of fill.

Jan 1, 1988

By E. F. Divers

In response to a request from the Mine Safety and Health Administration, the Bureau of Mines has recently completed a respirable dust survey of 18 U.S. coal preparation plants. Of these, three were essentially free of dust problems. Respirable dust exposure of workers in the remaining plants depended on the time spent in the dusty areas. In five of the plants surveyed, Bureau tests showed that in some areas worker exposures could exceed Federal dust limits in less than 2 hours.

Jan 1, 1988

By W. E. Wallace, P. S. Mike, C. A. Hill, V. Vallyathan, M. J. Keane

Respirable quartz duet and a kaolin clay dust have been found to be of comparable cytotoxic potential in vitro on a specific surface area basis (Wallace, et a1,1985), despite the distinctly different potentials of quartz and clay for causing pneumoconiosis or pulmonary fibrosis (Sheers, 1984). A respired particle depositing in a respiratory bronchiole or alveolus will contact a pulmonary surfactant hypophase, of which a primary component is diacyl glycerophosphorylcholine, or diacyl lecithin (DPL) (Clements, et al, 1970). Several studies have found that adsorption of such surfactant suppresses in vitro cytotoxic effects of quartz dust (Marks, 1957). Subsequent phagocytosis and digestion by a macrophage may remove the coating, restoring cytotoxic potential and initiating disease processes (Iles, 1979). Adsorption of dipalmitoyl lecithin (DPL) from emulsion in physiologic saline by respirable sized quartz dust and kaolin dusts, and consequent diminution of the dusts' hemolytic and macrophage cytotoxic potential have been reported (Wallace, et al, 1985). This report presents additional data on the cell-free in vitro phospholipase A2 enzymatic digestion of dipalmitoyl lecithin adsorbed on a quartz and a kaolin respirable sized dust (Wallace, et al, 1988) to investigate mineral specific differences in the rates of digestion and of consequent restoration of dust membranolytic potential. Respirable crystalline alpha quarts used was eighty percent smaller than 5 micorometer aerodynamic diameter with a nitrogen adsorption specific surface area of 3.97 m2/g. Respirable kaolin dust was ninety percent smaller than 5 micrometer diameter and had a specific surface area of 13.25 m2/g.

Jan 1, 1988

By Robert D. Pehlke

"Current continuous casting processes are going through a rapid evolution of advances and new developments. At the same time, intense efforts are being directed to the development of radical new technologies such as continuous casting of thin slabs and strip steel.Traditionally, the casting processes for steel have been anticipated by the development and implementation of processes in the non-ferrous industry. This trend is reviewed and what it may portend for steel is described.IntroductionThe continuous casting of steel has been a widely adopted process in the production of steel. The concepts for this processing go back into the early and mid 1800's; however, commerical development was delayed for a variety of reasons until the mid twentieth century.Beginning in the early 1960's, adoption of continuous casting was initiated and continues at this point in time to be accelerated. In Japan, more than 90% of the steel produced is continuously cast (1). More than 50% of the steel produced in the United States is continuously cast and this fraction continues to rise (2). Numerous examples can be cited of installations costing well over $200,000,000 which have provided a payoff in less than a year and a half. As this process has continued to be applied and its technology to increase, computer control systems have been installed. In particular, in the larger plants producing slabs, sophisticated computer systems involving the integration and networking of mini-computers, micro-computers, and mainframe including back-up systems at all levels are being utilized. Pehlke (3), and Harabuchi and Pehlke (4) have described the structure of these systems."

Jan 1, 1988

By K. Szafran, R. E. L. Seal, M. Tansey

Conversion of hydraulic equipment to fire resistant fluids has been hampered by less than satisfactory component performance and in some cases, catastrophic equipment failure. Concern over identifying possible causes to these problems led to a joint research project between the Potash Corporation of Saskatchewan Mining Limited and the University of Saskatchewan. This paper summarizes some of the results and conclusions derived from this joint project. In this study, the research was limited to evaluating the effects of potash contamination on the performance of hydraulic equipment. Two separate types of tests were conducted in order to provide a basis upon which trends could be established. This study concluded that the presence of potash dust in the hydraulic fluid can induce severe wear over relatively short periods of time. It was also deduced that a contaminant free fluid combined with proper fluid maintenance could extend the performance of hydraulic components using fire resistant fluids even under very severe operating conditions, such as elevated pressures and temperatures. Recommendations as to how to achieve this goal and the practicality of doing so are presented.

Jan 1, 1988

By Martin Hertzberg

This Bureau of Mines report analyzes diverse observations of the rates and mechanisms for the pyrolysis and devolatilization of coal and polymethylmethacrylate (PMMA). New data are presented for PMMA, together with new morphological evidence for the microscopic structure of the pyrolysis and devolatilization wave front in coals. It is concluded that there is no substantive evidence to support the traditional viewpoint that the pyrolysis and devolatilization rate process occurs isothermally, under chemical rate control; or is described realistically by a classical, unimolecular Arrhenius function of temperature. Instead, the reaction process occurs as a highly nonisothermal, heat-flux-driven, pyrolysis and devolatilization wave front, whose speed of propagation is predictable by internal heat transport constraints. Except for the complication of its charlayer residue, whose increasing thickness insulates the pyrolysis wave front from the heat source flux that drives it, both coal and PMMA behave similarly during pyrolysis and devolatilization. For PMMA, decomposition occurs at a temperature of 3500 to 5500 C; for coal it occurs at 4500 to 6000 C. There is no evidence that the reactant temperature ever exceeds those values regardless of the source temperature to which the samples are exposed.

Jan 1, 1988