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Geology topics

Carol J. Lind

Publications and source records attributed to Carol J. Lind.

15 recordsLinked to original sources
USGS2002

Hausmannite (Mn 3 O 4 ) conversion to manganite (γ-MnOOH) in dilute oxalate solution

Oxalic acid retards the alteration of Mn3O4 to γ-MnOOH during aging at pH 7.4 ?? 0.2 in well-aerated, abiotic suspensions that contain 4.4 ?? 10-3 M total Mn. In solutions of 1.25 ?? 10-3 M oxalate and greater, about 15% of the initial Mn3O4 altered to ??-MnOOH by day 10, and in solutions of 6.7 ?? 10-4 M oxalate, about 45% altered to ??-MnOOH by day 67. Although precipitation continued through day 365, the degree of conversion remained the same as at day 10 and day 67, respectively. In oxalate-free suspensions, the conversion was about 80% complete by day 67 and 100% by day 109. Oxalate complexed most of the dissolved divalent Mn, lowered the free Mn(II) and MnSO40 concentrations, but increased the total dissolved Mn. Steric hindrance of surface reactions by a suggested manganese oxalate layer on the Mn3O4 surface may explain the blockage of the oxidation cycle.

Environmental Science & Technology↗
USGS1998

In-situ alteration of minerals by acidic ground water resulting from mining activities: Preliminary evaluation of method

The chemical composition of the Cu-mining-related acidic ground water (pH ∼ 3.5 to near neutral) in Pinal Creek Basin, Arizona has been monitored since 1980. In-situ experiments are planned using alluvial sediments placed in the ground-water flow path to measure changes in mineral and chemical composition and changes in dissolution rates of subsurface alluvial sediments. The test results should help refine developed models of predicted chemical changes in ground-water composition and models of streamflow. For the preliminary test, sediment from the depth of the well screen of a newly drilled well was installed in three wells, the source well (pH 4.96) and two up-gradient wells (pHs 4.27 and 4.00). The sediment was placed in woven macrofilters, fastened in series to polyvinyl chloride (PVC) pipes, and hung at the screened level of each well. After interacting with the slowly moving ground water for 48 days, the test sediments were removed for analysis. There was no evidence that any of the materials used were biologically or chemically degraded or that the porosity of the filters was diminished by ferric hydroxide precipitation. These materials included 21-μm-pore (21PEMF) and 67-μm-pore polyester and the 174-μm-pore fluorocarbon Spectra/mesh macrofilters containing the in-situ sediment, the polypropylene (PP) macrofilter support structures, and the Nylon (NY) monofilament line used to attach the samples to the PVC pipe. Based on chemical and mineral composition and on particle-size distribution of the sediment before and after ground-water exposure, the 21PEMF macrofilter was chosen as the most suitable macrofilter for the long-term in-situ experiment. Tests also showed that the PP support structures and the NY monofilament line were sufficiently durable for this experiment.

Arizona↗
USGS1997

Iron deposition as acidic groundwater encounters carbonates in the alluvium of Pinal Creek, Arizona, U.S.A.

In a column experiment, acidic groundwater from Pinal Creek Arizona, a Cu mining area, was eluted through a composited alluvial sample obtained from a core that had been removed from a well downgradient of the acidic groundwater. The minerals present in typical grains and flakes in the alluvium before and after the elution were determined by X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive multichannel analyses (EDX). The concentrations of Fe, Ti, Mn, Si, Al, Na, Ca, K, Mg and S in these grains and flakes and in their microcrystalline surface coatings were measured by EDX. In addition to magnetite, hematite, and Fe-Ti oxides, Fe was most concentrated in micas (especially biotite-like flakes) and in the microcrystalline coatings. The measured elements in these microcrystalline coatings were primarily K, Fe, Al, and Si. The microcrystalline coatings on the mica flakes also contained Mg. The approximate 1:3 Mg:Si atomic ratios (ARs) of the biotite-like flakes both before and after the elution would suggest that the Fe deposited during the elution had not substituted for Mg in these flakes. As a result of the elution, assuming no loss of Si, the averaged recorded Fe:Si AR of the microcrystalline coatings increased from (0,46 to 0.58):3.00. Iron deposition on the typical grains and flakes may relate to the presence of Fe in the particle on which it is deposited or to the presence of Fe in the microcrystalline surface coatings before elution. The data here are not sufficient for a statistical evaluation, but elution caused the following trends: (1) The Fe:Si A R increased in the (K,Fe,Al,Si)-microcrystalline surface coatings; (2) For the mica flakes, there was more than a 2-fold increase in the Fe:Si AR for the microcrystalline surface coatings of the Fe-rich biotite-like flakes but no measurable increase of the Fe:Si AR for the microcrystalline surface coatings of the muscovite-like flakes that contained 3-5 times less Fe; (3) Also for the biotite-like flakes, the increase in Fe:Si AR was greater in the flakes that had a higher Fe:Si AR; (4) The Fe deposition on the Fe-rich microcrystalline surface coatings of the feldspar was much greater than on the Fe-poor, beige quartz and feldspar grains that, prior to elution, had only CaSO4 microcrystalline coatings; and (5) No Fe was deposited on Fe-poor grains with no microcrystalline surface coating.

Arizona↗
USGS1994

Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP 2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO 3 ) 2 , when the experimental system was held between pH 8.5 and 9.0 while CO 2 -free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO 2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO 3 ), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn 4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for kutnahorite. Thermodynamic feasibilities of eight potential chemical reactions forming solid phases of interest were evaluated by calculating their respective reaction affinities attained during titration and aging. The results are in general agreement with the indications for the presence of these species given by X-ray and electron diffraction. The presence of carbonates in precipitated encrustations formed from groundwater below the land surface and their occurrence in manganese oxide crusts that precipitate from the creek water, also are predicted by these results.

Geochimica et Cosmochimica Acta↗
USGS1993

Manganese minerals and associated fine particulates in the streambed of Pinal Creek, Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O 2 is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed. Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek. In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn 3 O 4 to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO 3 and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn 4 O 9 · (3H 2 O)) and takanelite ((Mn,Ca)Mn 4 O 9 · (3H 2 O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO 3 from an anoxic groundwater that contained CO 2 HCO 3 , and precipitated Mn 3 O 4 and subsequently MnOOH from an oxic surface water from which most of the dissolved CO 2 had been removed. It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the Mn Fe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO 3 , 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.

Applied Geochemistry↗
USGS1991

Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn 2+ and Cd 2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd 2 Mn 3 4+ O 8 , Mn 2+ 2 Mn 4+ 3 O 8 , MnO 2 (ramsdellite), and CdCO 3 . Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn 2+ Mn 2 3+ O 4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35°C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn 4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn 4+ oxide formation in the presence of Cd 2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn 2 O 4 Int , an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd 2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn 3+ ions. The Mn 2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn 2+ to Mn 4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd 2 Mn 3 O 8 and MnO 2 increased at the expense of other precipitate components.

Geochimica et Cosmochimica Acta↗
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 &#x394;G coOOH 0 "> ΔGcoOOH0 of &#x2212;92.3 &#xB1; 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↗
USGS1983

Nonequilibrium models for predicting forms of precipitated manganese oxides

Manganese oxides precipitated by bubbling air through 0.01 molar solutions of MnCl 2 , Mn(NO 3 ) 2 , MnSO 4 , or Mn(ClO 4 ) 2 at a constantly maintained pH of 8.5 to 9.5 at temperatures of 25°C or higher consisted mainly of hausmannite, Mn 3 O 4 . At temperatures near 0°C, but with other conditions the same, the product is feitknechtite, βMnOOH, except that if the initial solution is MnSO 4 and the temperature is near 0°C the product is a mixture of manganite, γMnOOH and groutite, αMnOOH. All these oxides are metastable in aerated solution and alter by irreversible processes to more highly oxidized species during aging. A two-step nonequilibrium thermodynamic model predicts that the least stable species, βMnOOH, should be most readily converted to MnO 2 . Some preparations of βMnOOH aged in their native solution at 5°C attained a manganese oxidation state of +3.3 or more after 7 months. Hausmannite aged at 25°C altered to γMnOOH. The latter is more stable than a or βMnOOH, and manganese oxidation states above 3.0 were not reached in hausmannite precipitates during 4 months of aging. Initial precipitation of MnCO 3 rather than a form of oxide is likely only where oxygen availability is very low. Composition of solutions and oxidation state and morphology of solids were determined during the aging process by chemical analyses, X-ray and electron diffraction and transmission electron micrographs.

Geochimica et Cosmochimica Acta↗
USGS1975

Effects of organic solutes on chemical reactions of aluminum

Concentrations of organic matter in the general range of 1-10 milligrams per litre organic carbon are common in natural water, and many naturally occurrin7 organic compounds form aluminum complexes. The aluminum concentrations in near-neutral pH solutions may be 10-100 times higher than the values predicted from solubility data if formation of such organic complexes is ignored. The processes of polymerization of aluminum hydroxide and precipitation of gibbsite are inhibited by the presence of the organic flavone compound quercetin in concentrations as low as 10 x -5.3 mole per litre. Quercetin forms a complex, with a probable molar ratio of 1:2 aluminum to quercetin, that has a formation constant (f12) of about 10 12. A complex with a higher aluminum-quercetin ratio also was observed, but this material tends to evolve into a compound of low solubility that removes aluminum from solution. In the presence of both dissolved aluminum and aqueous silica, low concentrations of quercetin improved the yield of crystallized kaolinite and halloysite. Small amounts of well-shaped kaolinite and halloysite crystals were identified by electron microscopy in solutions with pH's in the range 6.5-8.5 after 155 days aging in one experimer t and 481 days aging in a repeated experiment. The bulk of the precipitated material was amorphous to X-rays, and crystalline material was too small a proportion of the total to give identifiable X-ray diffraction peaks. The precipitates had aluminum-silicon ratios near 1, and their solubility corresponded to that found by Hem, Roberson, Lind, and Polzer (1973) for similar aluminosilicate precipitated in the absence of organic solutes. The improved yield of crystalline material obtained in the presence of quercetin probably is the result of the influence of the organic compound on the aluminum hydroxide polymerization process. Natural water containing color imparted by organic material tends to be higher in aluminum than would be predicted by pH, silica concentrations, and solubility data for inorganic aluminum species.

Water Supply Paper↗
USGS1974

Kaolinite synthesis at 25°C

The addition of quercetin, an organic flavone (C 15 H 10 O 7 ), to aqueous solutions containing silica and aluminum and adjusted to final p H's from 6.5 to 8.5 produced a 1 : 1 alumninosilicate precipitate which, after 6 to 16 months of aging in solution at 25&deg;C, contained as much as 5 percent well-formed kaolinite plates. Similar solutions containing no organic material produced relatively amorphous precipitates with the same composition and stability (standard free energy of formation = -897&plusmn;1 kilocalories per mole) but with substantially smaller amounts of crystaline material even after 2 years of aging.

Science↗
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↗