Mineral resource of the Month: Clay
Clays were one of the first mineral commodities used by people. Clay pottery has been found in archeological sites that are 12,000 years old, and clay figurines have been found in sites that are even older.
SEARCH · Search USGS
Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Clays were one of the first mineral commodities used by people. Clay pottery has been found in archeological sites that are 12,000 years old, and clay figurines have been found in sites that are even older.
Clays represent one of the largest mineral commodities in the world in terms of mineral and rock production and use. Many people, however, do not recognize that clays are used in an amazingly wide variety of applications. Use continues to increase worldwide as populations and their associated needs increase. Robert Virta, clay and shale commodity specialist for the U.S. Geological Survey, has prepared the following information about clays.
To assess the presence and distribution of a variety of hydro-phobic chemicals in streams in the Red River of the North Basin, bottom sediments were analyzed for trace elements, organochlorines, and polycyclic aromatic hydrocarbons (PAHs). Glaciolacustrine clays and carbonate minerals are common in fine sediments of the region, and can help explain the distribution of many elements. Aluminum (Al), an indicator of glaciolacustrine clay minerals, correlates strongly (r>0.75, p<0.05) with Cr, Co, Fe, La, Li, K, Sc, and Ti; and moderately (0.55<r<0.75) with Ce, Cu, Ga, Nd, Ni, Th, V, and Y. Excluding the tributary Pembina River Basin, Eu, Nb, Ce, La, Nd, and Ni also have strong correlations with Al. Al correlates negatively with major elements associated with carbonate minerals (Ca, Mg, and inorganic carbon). No significant correlations with Al, Ca, or Mg were observed for As, Pb, Mn, Hg, Se, or Ag, which implies that these elements have different environmental sources or behaviors than glaciolacustrine clays or carbonate minerals. Reduction-oxidation processes may influence Mn distribution. Lead (Pb) and mercury (Hg) are known to be anthropogenically enriched in the environment--their distribution may indicate environmental enrichment in Red River of the North Basin streams. Organochlorines detected are limited to traces of DDT and its metabolites (mostlyp,p'-DDE). Fourteen PAHs, which are constituents of fossil fuels and of combustion byproducts, were detected in at least halfthe sediment samples; pyrene and fluoranthene were detected in about 90 percent of samples. The contaminants detected in this study were present at low levels, likely indicative of diffuse or remote sources; they occur widely in the environment.
Maximum concentrations of lithium found in samples of flint clay and associated rocks of Pennsylvanian age in different States, in parts per million (ppm), are: Missouri, 5100; Pennsylvania-Maryland, 2100; Kentucky, 890; Ohio, 660; Alabama, 750; and Illinois, 160. Lithium-bearing kaolin deposits are distributed in the Coastal Plain province from New Jersey to Texas, and one occurs in Idaho; maximum lithium concentrations in samples from these deposits range from 64 to 180 ppm. The maximum concentration found in the Arkansas bauxite region is 460 ppm and that in flint clay in Colorado is 370 ppm. Samples from areas other than Pennsylvania, Maryland, Kentucky and Missouri are relatively few in number, represent mostly commercially valuable clays, and represent only a part of the refractory clay deposits in the United States. Data are not available on the clays associated with these deposits that may be unusable because they contain too much lithium as well as other deleterious elements. In both Pennsylvania and Missouri, lithium contents vary regionally between districts and locally between deposits. In samples containing more than 2000 ppm lithium, the lithium occurs in a dioctahedral chlorite mineral very similar to cookeite, which previously has not been recognized in sedimentary clays. The associated clays consist chiefly of well-crystallized kaolinite. The dioctahedral chlorite, however, seems to be most abundant where diaspore and boehmite occur along with the kaolinite. Barium, chromium, copper, phosphorus and strontium are present in some samples in amounts of several hundred pans per million or more, and may contribute to the failure of some clays to perform satisfactorily in firing tests. Lithium-rich clays could serve as a significant lithium resource in the very distant future. Clays that contain as much as 1% lithium may be common enough in Missouri or in Pennsylvania to be produced as a by-product to help support benefication costs for refractory clays. Sufficient amounts of lithium-rich clay may be found in deposits that have been explored, found unsatisfactory for normal refractory uses, and not developed. The lithium-rich clay in some deposits presently being worked may be worth stockpiling for eventual use.
This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays. The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley”" clay). The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality. The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay. Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.
Slag is a by-product of steel manufacturing and a ubiquitous fill material in northwestern Indiana. Ground water associated with slag deposits generally is characterized by high pH and elevated concentrations of many inorganic water-quality constituents. The U.S. Geological Survey, in cooperation with the Indiana Department of Environmental Management, conducted a study in northwestern Indiana from June 1995 to September 1996 to improve understanding of the effects of slag deposits on the water quality of a glacial-outwash aquifer. The Bairstow Landfill, a slag-fill deposit overlying the Calumet aquifer near Hammond, Indiana, was studied to represent conditions in slag-deposit settings that are common in northwestern Indiana. Ground water from 10 observation wells, located in four nests at the site, and surface water from the adjacent Lake George were analyzed for values of field-measured parameters and concentrations of major ions, nutrients, trace elements, and bulk properties. Solid-phase samples of slag and aquifer sediment collected during drilling were examined with X-ray diffraction and geochemical digestion and analysis. Concentrations of calcium, potassium, sodium, and sulfate were highest in wells screened partly or fully in slag. Potassium concentrations in ground water ranged from 2.9 to 120 milligrams per liter (mg/L), were highest in water from slag deposits, and decreased with depth. The highest concentrations for aluminum, barium, molybdenum, nickel, and selenium were in water from the slag. Silica concentrations were highest in wells screened directly beneath the slag-aquifer interface, and magnesium concentrations were highest in intermediate and deep aquifer wells. Silica concentrations in shallow and intermediate aquifer wells ranged from 27 to 41 mg/L and were about 10 times greater than those in water from slag deposits. The highest concentrations for chromium, lead, and zinc were in ground water from immediately below the slag-aquifer interface. The solid-phase analyses indicated that calcite, dolomite, and quartz generally were present throughout the slag-aquifer system; barian celestite, cristobalite, manganese-bearing calcite, and minrecordite were present in fewer samples. Trace elements that are liberated from the slag may be incorporated as impurities during precipitation of major minerals, sorbed onto clays and other grainsize fractions not analyzed as part of this study, or present in low-abundance minerals that were not detected by the X-ray analysis. Mass-balance and speciation programs were used to identify geochemical processes that may be occurring as water infiltrates through the slag, flows into the aquifer, and discharges into Lake George. The geochemical models indicate that precipitation of calcite may be occurring where slag-affected water enters the aquifer. Models also indicate that dolomite precipitation and clay-mineral dissolution may be occurring at the slag-aquifer interface; however, dolomite precipitation is generally believed to require geologically long time periods. Silica may be dissolving where slag-affected ground water enters the aquifer and may be precipitating where slag-affected ground water discharges to the lakebed of Lake George. In addition to the site-specific study, a statistical analysis of regional water quality was done to compare ground water in wells affected and unaffected by slag. When com-pared to wells in background locations in the Calumet aquifer, wells screened in slag across northwestern Indiana and northeastern Illinois generally had relatively higher pH and specific-conductance values and relatively higher concentrations of alkalinity, dissolved solids, suspended solids, total organic carbon, calcium, potassium, sodium, chloride, aluminum, barium, and possibly magnesium, sulfate, chromium, cobalt, copper, cyanide, manganese, mercury, nickel, and vanadium. When compared to wells in slag and wells in background locations, ground water from immediately beneath or immediately downgradient from slag had relatively high concentrations of arsenic and silica. Water-quality characteristics in ground water at the Bairstow Landfill were similar to water-quality characteristics in slag-contact and slag-affected wells throughout northwestern Indiana.
Vermiculite comprises a group of hydrated, laminar magnesium-aluminum-iron silicate minerals resembling mica. They are secondary minerals, typically altered biotite, iron-rich phlogopite or other micas or clay-like minerals that are themselves sometimes alteration products of amphibole, chlorite, olivine and pyroxene. Vermiculite deposits are associated with volcanic ultramafic rocks rich in magnesium silicate minerals, and flakes of the mineral range in color from black to shades of brown and yellow. The crystal structure of vermiculite contains water molecules, a property that is critical to its processing for common uses. Using a process called exfoliation-in which vermiculite flakes are heated to 900 degrees Celsius or higher, causing water within the flakes to flash to steam and expand-crude vermiculite ore is processed into particles that are eight to 20 times larger. The resulting lightweight material is chemically inert and fire resistant, with low density and low thermal conductivity. It is also odorless, has high liquid absorption capacity and catalytic properties. Because it is lightweight and thermally insulating, vermiculite is used in general building plasters and concrete products, alone or combined with other lightweight aggregates such as perlite. Special plasters, in which vermiculite is combined with binders like gypsum or portland cement, fillers or other additives, provide fire protection and soundproofing. As insulation, exfoliated vermiculite, sometimes treated with a water repellent, is used to fill pores and cavities in masonry construction and hollow blockwork to enhance acoustic properties, fire rating and insulation performance. Exfoliated vermiculite can also be used to produce refractory and insulation concretes and mortars, and to make high-temperature binders for construction materials, gaskets, specialty papers, textiles and vehicle brake linings. Finer grades of exfoliated vermiculite can be used to produce various shapes of insulation pellets, high-temperature insulation, as a primary component in cementitious coatings, and as a filler in inks, paints, plastics and other materials. Vermiculite can absorb liquids such as fertilizers, herbicides and insecticides, which can then be transported as free-flowing solids. It is used in the fertilizer and pesticide markets because of its ability to act as a bulking agent, carrier and extender. In horticulture, exfoliated vermiculite improves soil aeration and moisture retention, and when mixed with peat or other composted materials, such as pine bark, vermiculite produces a good growing medium for plants. As a soil conditioner, exfoliated vermiculite improves aeration in clay-rich soils and water retention in sandy soils, while reducing the likelihood of compaction, cracking and crusting of the soil. For more information on the commercial use of vermiculite, visit minerals.usgs.gov/minerals/ .
Vermiculite comprises a group of hydrated, laminar magnesium-aluminum-iron silicate minerals resembling mica. They are secondary minerals, typically altered biotite, iron-rich phlogopite or other micas or clay-like minerals that are themselves sometimes alteration products of amphibole, chlorite, olivine and pyroxene. Vermiculite deposits are associated with volcanic ultramafic rocks rich in magnesium silicate minerals, and flakes of the mineral range in color from black to shades of brown and yellow. The crystal structure of vermiculite contains water molecules, a property that is critical to its processing for common uses.
Weathering products formed on surfaces of both potassium and plagioclase feldspar (An 70 ), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7.21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite . 4H 2 O. The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.
The mineral surface of Wyoming bentonite (clay) was modified by replacing inorganic ions by each of 10 quaternary ammonium compounds, and tetrachloromethane sorption to the modified sorbents from water was studied. Tetrachloromethane sorption from solution to clay modified with tetramethyl-, tetraethyl-, benzyltrimethyl-, or benzyltriethylammonium cations generally is characterized by relatively high solute uptake, isotherm nonlinearity, and competitive sorption (with trichloroethene as the competing sorbate). For these sorbents, the ethyl functional groups yield reduced sorptive capacity relative to methyl groups, whereas the benzyl group appears to have a similar effect on sorbent capacity as the methyl group. Sorption of tetrachloromethane to clay modified with dodecyldimethyl(2-phenoxyethyl)-, dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, or benzyldimethylhexadecylammonium bromide is characterized by relatively low solute uptake, isotherm linearity, and noncompetitive sorption. For these sorbents, an increase in the size of the nonpolar functional group(s) causes an increase in the organic carbon normalized sorption coefficient (Koc). No measurable uptake of tetrachloromethane sorption by the unmodified clay or clay modified by ammonium bromide was observed.
The influence of clay units on ground-water composition was investigated in a heterogeneous carbonate aquifer system of Miocene age in southwest Florida, known as the Intermediate aquifer system. Regionally, the ground water is recharged inland, flows laterally and to greater depths in the aquifer systems, and is discharged vertically upward at the saltwater interface along the coast. A depth profile of water composition was obtained by sampling ground water from discrete intervals within the permeable carbonate units during coring and by squeezing pore water from a core of the less-permeable clay layers. A normative salt analysis of solute compositions in the water indicated a marine origin for both types of water and an evolutionary pathway for the clay water that involves clay diagenesis. The chemical composition of the ground water in the carbonate bedrock is significantly different from that of the pore water in the clay layers. Dissolution of clays and opaline silica results in high silica concentrations relative to water in other parts of the Intermediate aquifer system. Water enriched in chloride relative to the overlying and underlying ground water recharges the aquifer inland where the confining clay layer is absent, and it dissolves carbonate and silicate minerals and reacts with clays along its flow path, eventually reaching this coastal site and resulting in the high chloride and silica concentrations observed in the middle part of the Intermediate aquifer system. Reaction-path modeling suggests that the recharging surficial water mixes with sulfate-rich water upwelling from the Upper Floridan aquifer, and carbonate mineral dissolution and precipitation, weathering and exchange reactions, clay mineral diagenesis, clay and silica dissolution, organic carbon oxidation, and iron and sulfate reduction result in the observed water compositions.
Reinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K + . In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. The progressive loss of radiogenic argon in the deepest zone yielded a constant apparent age for the clays with depth, an effect previously attributed to “punctuated diagenesis.” The above hypothesis for illite formation emphasizes the need to establish the zone (i.e., the reaction mechanism) from which shales were derived before making detailed geologic interpretations based on illite mineralogy.
Black shale is a dark-colored mudrock containing organic matter that may have generated hydrocarbons in the subsurface or that may yield hydrocarbons by pyrolysis. Many black shale units are enriched in metals severalfold above expected amounts in ordinary shale. Some black shale units have served as host rocks for syngenetic metal deposits. Black shales have formed throughout the Earth's history and in all parts of the world. This suggests that geologic processes and not geologic settings are the controlling factors in the accumulation of black shale. Geologic processes are those of deposition by which the raw materials of black shale are accumulated and those of diagenesis in response to increasing depth of burial. Depositional processes involve a range of relationships among such factors as organic productivity, clastic sedimentation rate, and the intensity of oxidation by which organic matter is destroyed. If enough organic material is present to exhaust the oxygen in the environment, black shale results. Diagenetic processes involve chemical reactions controlled by the nature of the components and by the pressure and temperature regimens that continuing burial imposes. For a thickness of a few meters beneath the surface, sulfate is reduced and sulfide minerals may be deposited. Fermentation reactions in the next several hundred meters result in biogenic methane, followed successively at greater depths by decarboxylation reactions and thermal maturation that form additional hydrocarbons. Suites of newly formed minerals are characteristic for each of the zones of diagenesis.
Trace element data from 59 Pliocene lignite cores from the lignite field in the Kosovo Basin, southern Serbia, show localized enrichment of Ni and Cr (33-304 ppm and 8-176 ppm, respectively, whole-coal basis). Concentrations of both elements decrease from the western and southern boundaries of the lignite field. Low-temperature ash and polished coal pellets of selected bench and whole-coal samples were analyzed by X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray analyses. These analyses show that most of the Ni and Cr are incorporated in detrital and, to a lesser degree, in authigenic minerals. The Ni- and Cr-bearing detrital minerals include oxides, chromites, serpentine-group minerals and rare mixed-layer clays. Possible authigenic minerals include Ni-Fe sulfates and sulfides. Analyses of three lignite samples by a supercritical fluid extraction technique indicate that some (1-11%) of the Ni is organically bound. Ni- and Cr-bearing oxides, mixed-layer clays, chromites and serpentine-group minerals were also identified in weathered and fresh samples of laterite developed on serpentinized Paleozoic peridotite at the nearby Glavica and C??ikatovo Ni mines. These mines are located along the western and northwestern rim, respectively, of the Kosovo Basin, where Ni contents are highest. The detrital Ni- and Cr-bearing minerals identified in lignite samples from the western part of the Kosovo Basin may have been transported into the paleoswamp by rivers that drained the two Paleocene laterites. Some Ni may have been transported directly into the paleoswamp in solution or, alternatively, Ni may have been leached from detrital minerals by acidic peat water and adsorbed onto organic matter and included into authigenic mineral phases. No minable source of Ni and Cr is known in the southern part of the lignite field; however, the mineral and chemical data from the lignite and associated rocks suggest that such a source area may exist.
Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence that makes up part of the Eocene Siletz River Volcanics in the central Coast Range, Oregon. Regional zoning of zeolite assemblages is not apparent; the zeolites formed in joints, fractures, and interstices, although most occur in central cavities of basalt pillows. The zeolites and associated minerals identified, in general order of paragenetic sequence, are smectite, pyrite, calcite (small spheres), thomsonite, natrolite, analcime, scolecite, mesolite, stilbite, heulandite, apophyllite, chahazite, mordenite, calcite (scalenohedra and twinned rhombohedra), laumontite, and amethystine quartz. Common three-mineral assemblages are: natrolite-analcime-sfilbite, stilbite-heulandite-chabazite, stilbite-apophyllie-chabazite, and natrolite-mesolite-laumontite. Alteration of basaltic glass, which was initially abundant, appears to have been an important factor in formation of the zeolites. Isotopic data suggest that zeolitization occurred during a low-temperature (60 ~ 70°C submarine hydrothermal event, or by reactions of cold (~ 10°C meteoric water with basalt over a long time. The occurrence of different mineral assemblages in cavities of adjacent basalt pillows indicates that these minerals crystallized in dosed systems that were isolated as fractures and joints were sealed by deposition of smectite and early zeolites. Although the total chemical composition of the mineral assemblages in cavities is similar, different mineral species formed because of the sensitivity of zeolite minerals to slight variations in physical and chemical conditions within individual cavities.
The implication by Murthy and Ferrell (1972)that interstitial water studies are in a confused state is criticized on the basis that the authors have not drawn on a considerable body of data, especially Soviet studies since the 1950's, and results of the Deep Sea Drilling Project. Pressure filtration systems for extracting interstitial waters are currently the methods of choice for marine studies and have achieved substantial reliability and reproducibility. Although gaps and problems remain, many aspects of interstitial composition of marine sediments have been clarified; these include the substantial constancy of composition of interstitial waters in deep sea pelagic deposits, depletion of interstitial cations owing to authigenic mineral formation in more rapidly accumulated (especially terrigenous) sediments, and special phenomena in sediments overlying salt deposits.
The coarse, non-clay fraction of many flint-like kaolinitic claystones often contains mineral grains diagnostic of the claystone's origin and, in the case of tonsteins (altered volcanic ashes), may also provide minerals suitable for radiometric dating. Separation of the non-clay mineral fraction is often difficult because flint clays and flint-like clays resist slaking in water and thus are difficult to disaggregate. Chemical disaggregation of resistant kaolinitic claystones may be achieved by immersion in either hydrazine monohydrate or DMSO for periods ranging from one day to several weeks. Generally, hydrazine monohydrate works more quickly and efficiently than DMSO to disaggregate most kaolinitic claystones and flint clays.
Mid-infrared spectroscopy (2.5-50 /µm) has been extensively used to identify and characterize clays and associated minerals in rocks and soils, with particular emphasis on the 3-, 10-, and 20-/µm regions (Farmer and Russell, 1967; Farmer, 1968; White, 1971; Van der Marel and Beutelspacher, 1976). However, application of mid-infrared spectroscopy in remote-sensing activities has been restricted because the spectral information occurs only as a small perturbation to the emitted radiation from the earth's surface, and much of that which is especially relevant to clays (e.g., the 3.0-µm region) is obscured by atmospheric absorption.