Geology topics

C. E. Roberson

Publications and source records attributed to C. E. Roberson.

11 recordsLinked to original sources

USGS1989

Coprecipitation and redox reactions of manganese oxides with copper and nickel

Open-system, continuous-titration experiments have been done in which a slow flux of ∼0.02 molar solution of Mn 2+ chloride, nitrate, or perchlorate with Cu 2+ or Ni 2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu 2 Mn 3 O 8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, βMnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO 2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included βMnOOH, Ni(OH) 2 , and the same two forms of MnO 2 . The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu 2+ and Ni 2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems.

Geochimica et Cosmochimica Acta↗

USGS1987

Synthesis and stability of hetaerolite, ZnMn2O4, at 25°C

A precipitate of nearly pure hetaerolite, ZnMn 2 O 4 , a spinel-structured analog of hausmannite, Mn 3 O 4 , was prepared by an irreversible wprecipitation of zinc with manganese at 25°C. The synthesis technique entailed constant slow addition of a dilute solution of Mn 2+ and Zn 2+ chlorides having a Mn/Zn ratio of 2:1 to a reaction vessel that initially contained distilled deionized water, maintained at a pH of 8.50 by addition of dilute NaOH by an automated pH stat, with continuous bubbling of CO 2 -free air. The solid was identified by means of X-ray diffraction and transmission electron microscopy and consisted of bipyramidal crystals generally less than 0.10 μm in diameter. Zn 2+ ions are able to substitute extensively for Mn 2+ ions that occupy tetrahedral sites in the hausmannite structure. Hetaerolite appears to be more stable than hausmannite with respect to spontaneous conversion to γMnOOH. The value of the standard free energy of formation of hetaerolite was estimated from the experimental data to be −289.4 ± 0.8 kcal per mole. Solids intermediate in composition between hetaerolite and hausmannite can be prepared by altering the Mn/Zn ratio in the feed solution.

Geochimica et Cosmochimica Acta↗

USGS1985

Thermodynamic stability of CoOOH and its coprecipitation with manganese

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO 3 ) 2 held at pH 9.0 and 25°C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co 3 O 4 and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co 2+ activities and by redox potential measurements and gave a ΔG coOOH 0 "> ΔGcoOOH0 of −92.3 ± 0.5 kcal/mole "> −92.3 ± 0.5 kcal/mole . This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained βMnOOH, MnO 2 (birnessite) and CoOOH.

Geochimica et Cosmochimica Acta↗

USGS1984

Time and the crystallization of apatite in seawater

Carbonate fluorapatite has been synthesized in seawater in an experiment of nearly 10-years duration. The addition of phosphate to seawater whose fluoride concentration had been increased to 7.6 mg/l brought about an initial amorphous phosphate precipitate. After 20 months, a crystalline magnesium phosphate phase developed within the amorphous phosphate. Crystallization of apatite, which occurred during the last 3 years of the experiment, was accompanied by dissolution of the crystalline magnesium phosphate phase. The MgO content of the apatite (1.9 percent) is high in comparison to Tertiary and older apatite but similar to some young apatite; the CO 2 content (3.6 percent) is medium, and the fluorine content (2.2 percent) is low but again similar to some young apatite. The hydroxyl ion (OH − ) likely fills the need for additional fluorine-position atoms. The mole ratio of Ca plus substituent elements to P plus substituent elements (1.50) is low in comparison to the expected ratio of 1.67. The substitution of the hydronium ion (H 3 O + ) for Ca may account for this difference. The synthesis of apatite in seawater demonstrates that the factor of time overcomes the well known inhibiting effect of magnesium upon the crystallization of apatite. It also implies that given an adequate supply of phosphate, apatite can form in most ocean environments and likely plays a major pan in the control of the phosphate content of seawater.

Geochimica et Cosmochimica Acta↗

USGS1978

Stability of fluoride complex with silica and its distribution in natural water systems

Fluoride reacts with silicic acid to form SiF 2− 6 . A fluoride electrode was used to obtain an equilibrium constant of 10 30.18 for the reaction: Si(OH) 0 6 + 6 F − +4 H + = SiF 2− 6 + 4 H 2 O "> Si(OH)06+ 6F−+4H+=SiF2−6+ 4H2O at 25°C Although there may be some experimental evidence for existence of traces of species containing less than six F − ions per silicon ( n = 6), the species SiF 2− 6 predominates for n values from about 0.1 to 6. Silicic-acid complexing with fluoride is important only in solutions which have rather low pH and low concentrations of other cations which compete with silicon for fluoride. Computations for cold volcanic condensates from Hawaii indicate that for some samples much of the silicon is complexed by fluoride as SiF 2− 6 . However, in most cooled acidic natural water samples Al and Fe are more important than Si in complexing fluoride.

Chemical Geology↗

USGS1977

Solubility of natural fluorite at 25°C

The solubility products of two samples of natural fluorite from Rosiclare, Ill., and from Madoc, Ontario, were determined at 25°C by analyses of calcium and fluoride in sodium perchlorate solutions of varying ionic strength over a period of 3 years. Calcium concentrations were analyzed by atomic absorption spectrophotometry, fluoride concentrations were measured colorimetrically, and fluoride activities were measured using a specific ion electrode. The solubility products at the end of 3 years were determined by extrapolation to zero ionic strength. The final solubility product was found to be 10 -10.58±0.17 .

Journal of Research of the U.S. Geological Survey↗

USGS1973

Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.

Water Supply Paper↗

USGS1973

Fluorite equilibria in thermal springs of the Snake River Basin, Idaho

Some thermal water sources of the Snake River basin, Idaho, are near saturation with respect to fluorite. That mineral was identified by X-ray diffraction in precipitates induced in three water samples by adding sodium fluoride. The derived solubility product (K S0 ) for zero ionic strength was close to that calculated from Latimer's thermodynamic data (10 -9.7 7 ). The relative ease of precipitation of fluorite from these water samples indicates that equilibrium with respect to fluorite may occur in some ground-water systems.

Idaho↗

USGS1973

Solubility of cryolite at 25° C and 1 atmosphere pressure

For natural cryolite from Greenland the activity product for the reaction (in water), Na 3 Al F 6 c --> 3Na + + Al 3+ + 6F - , was found to be 10 -34.3 +/- 0.1 . This is in good agreement with earlier work in which equilibrium was approached from supersaturation.

Journal of Research of the U.S. Geological Survey↗

USGS1968

Activity product constant of cryolite at 25°C and one atmosphere using selective-ion electrodes to estimate sodium and fluoride activities

The activity product constant of cryolite (Na 3 AlF 6 ) at 25°C and 1 atm total pressure was calculated from data for solutions from which synthetic cryolite or mixtures of cryolite and a solid apparently related to ralstonite had precipitated. The activities of fluoride and of sodium were estimated using specific ion electrodes. The activity of Al 3+ was calculated from aluminum concentrations using equations which involve aluminum species existing in water solutions containing fluoride and hydroxide ions. For the reaction Na 3 AlF 6 ( c ) = 3 Na ( aq ) + + Al 3+ ( aq ) + 6 E - ( aq ) the activity product constant K so is 10 −33.84 , and the standard free energy of formation at 25°C is -745.4±1.0 kcal mole −1 . This latter is identical to a value from the literature which is based on calorimetric data. Although cryolite and related minerals are easily precipitated in the laboratory, their relative scarcity in nature suggests that the effect of influences, perhaps solutes other than those occurring in the structure, may inhibit or prevent the formation of cryolite.

Geochimica et Cosmochimica Acta↗

USGS1961

Aqua de Ney, California, a spring of unique chemical character

The chemistry of water of Aqua de Ney, a cold spring of unusual character located in Siskiyou County, Calif., has been re-examined as part of a study of the relation of water chemistry to rock environment. The water has a pH of 11·6 and a silica content of 4000 parts per million (p.p.m.), the highest values known to occur in natural ground waters. The rocks exposed nearby consist of two volcanic sequences, one predominantly basaltic in composition, the other highly siliceous. Neither these rocks nor the sedimentary and igneous rocks presumed to underlie the area at depth seem to offer explanation of the unusual mineralization which includes 240 p.p.m. of boron, 1000 p.p.m. of sulphide (as H 2 S), and 148 p.p.m. of ammonia nitrogen (as NH 4 ) in a water that is predominantly sodium chloride and sodium carbonate in character. By analogy, it is assumed that water from Aqua de Ney is the product of an initial mixture of connate sea water with a calcium magnesium sulphate water. It is postulated that ion exchange has increased the content of sodium and reduced that of calcium and magnesium, and that sulphate reduction has brought about the high alkalinity, high pH, and high content of sulphide. The large silica value is explained as the result of solution of silica by water having the high pH observed.

California↗