Ion exchangers in analytical chemistry

Mode of access: Internet.

Directions for laboratory work in physiological chemistry.

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Availability and chemistry of ground water on the Bruneau Plateau and adjacent eastern plain in Twin Falls County, south-central Idaho /

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Recent advances in general chemistry.

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Introduction to general chemistry. A graded course of one hundred lectures with an atlas of eighty plates, representing chemists, institutions, prime materials, crystals, diagrams and apparatus; and illustrations in the text

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Water chemistry controls on minor elemental concentrations and strontium isotopic compositions of freshwater biogenic carbonate in northeastern Washington streams

Tracking the movement of migratory freshwater fish is essential to those invested in rebuilding declining fish populations. Using strontium isotopic signatures to match calcified fish tissues to streams where fish spawn is a useful method of tracking migratory fish where physical tracking methods such as radio, acoustic, or external tags, have proven unsuccessful. In this study, we develop tools to practice this method of tracking fish in Lake Roosevelt and its upstream tributaries in Washington State by analyzing the elemental concentrations and 87Sr/86Sr ratios of water samples, and mussel shell samples. This study evaluates whether mussel shells act as an appropriate proxy for water chemistry by comparing the 87Sr/86Sr isotope ratios of water samples to the 87Sr/86Sr isotope ratios of mussel shells sampled from the same, or nearby, locations. We compare concentrations of Ba, Ca, Cd, Cu, Fe, Mg, Pb, Sr, and U in the water and mussel shell samples to determine the feasibility of using mussel shells as a proxy for water chemistry. If it is determined that the concentrations of these elements in mussel shells reflect that of the surrounding water composition, the elemental composition of mussel shells can be compared to that of calcified tissues in fish, such as otoliths, to infer the location of the natal stream. We report analyses of water and mussel shell samples collected from Lake Roosevelt, Sanpoil River, Spokane River, Colville River, Kettle River, Pend Oreille River, Kootenay River, and Columbia River in Washington State. Each of these rivers is a tributary to Lake Roosevelt, and each flows through different geologic units. We hypothesize that the differences in the rock units of each stream’s watershed are reflected in the elemental concentrations and strontium isotopic ratios of water in each stream and in the lake. We also hypothesize that the composition of the mussel shells will match the composition of the water samples, therefore allowing us to use the mussel shells as a proxy for local water chemistry. Additionally, we hypothesize that the composition of the mussel shells will vary by location, and that we will be able to then infer where a fish is from by matching the composition of the fish in question to the mussels we have analyzed. We found that 87Sr/86Sr values for water and mussel hinge samples collected from tributaries east of Lake Roosevelt are significantly higher than the 87Sr/86Sr values for samples collected from tributaries west of Lake Roosevelt with averages of 0.7235 and 0.7089, respectively. The average 87Sr/86Sr ratios for water and mussel hinge samples collected within Lake Roosevelt is 0.7158, which is between the averages for samples collected east and west of the lake. Generally, older rocks are exposed on the east side of the lake, and younger rocks on the west side of the lake, so our 87Sr/86Sr values support the hypothesis that geologic units are a primary control on water chemistry, and that tributary compositions mix to form an average weighed by flow in Lake Roosevelt. The 87Sr/86Sr values for water and mussel shell samples collected from the same locations have a strong, positive linear correlation, suggesting that mussel shell 87Sr/86Sr ratios reflect the 87Sr/86Sr ratios of the ambient water. With these data, we can distinguish between different streams and the lake, but cannot distinguish between samples from within the same stream or within Lake Roosevelt. The Sr:Ca and Fe:Ca ratios of water samples show positive correlations with mussel shell compositions, with R2 values of 0.82 and 0.52, respectively. Ratios of Mg, Ba, Cu, Cd, Pb, and U to Ca showed little or no positive correlation between water and mussel shell samples. The elemental concentration data collected for this study do not demonstrate whether a correlation between elemental ratios in water samples and elemental ratios in mussel shell samples collected from the same location exists. Positive Sr:Ca and Fe:Ca correlations for water versus mussel shell samples indicate that perhaps for some elements, the composition of mussel shells are representative of the composition of ambient water. Using elemental concentration ratios to complement 87Sr/86Sr isotopic data may enhance our ability to identify correlations between water and mussel shell samples, and ultimately between mussel shell and otolith samples. The hinge part of a mussel shell may be used as a proxy for local water composition because the mussel shell composition reflects that of the local ambient water. The hinge of the mussel has the same composition as the whole mussel shell. We measured variation of 87Sr/86Sr ratios in the water among different streams and Lake Roosevelt. The 87Sr/86Sr values for samples collected in tributaries east of Lake Roosevelt, which erode older rocks, are higher for mussel shell and water samples than the average 87Sr/86Sr values for mussel shell and water samples collected in tributaries west of Lake Roosevelt, which flow through younger rocks.

Chemistry of acid production in black coal mine washery wastes

Column leaching tests on black coal mine washery wastes were performed, to determine the chemistry of acid generation. Coal mine coarse rejects and tailings were subjected to wet and dry cycle dissolution and subsequently column leached. The rates of iron sulphide oxidation and carbonate mineral dissolution were determined based on the drainage chemistry. The kinetic data from column leach experiments are used to predict the time required to deplete the acid producing and acid consuming minerals in the mine wastes. The acid production in the mine rejects was found to depend upon iron chemistry, carbonate chemistry, diffusion of oxygen, and permeability. The chemistry of the drainage from two different coal mines is compared. (c) 2005 Elsevier B.V. All rights reserved.

Timing and chemistry of fluid-flow events in the Lawn Hill Platform, Northern Australia

Mudrocks and carbonates of the Isa superbasin in the Lawn Hill platform in northern Australia host major base metal sulfide mineralization, including the giant strata-bound Century Zn-Pb deposit. Mineral paragenesis, stable isotope, and K-Ar dating studies demonstrate that long-lived structures such as the Termite Range fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic in response to major tectonic events. Illite and chlorite crystallinity studies suggest the southern part of the platform has experienced higher temperatures (up to 300 degrees C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information oil the thermal regime in the basin and shows that clay formation was controlled not only by temperature increase with depth but also by high water/rock ratios along relatively permeable zones. K-Ar dating of illite, in combination with other data, may indicate three major thermal events in the central and northern Lawn Hill platform Lit 1500, 1440 to 1400, and 1250 to 1150 Ma. This study did not detect the earlier Century base metal mineralizing event at 1575 Ma. 1500 Ma ages are recorded only in the south and correspond to the age of the Late Isan orogeny and deposition of the Lower Roper superbasin. They may reflect exhumation of a provenance region. The 1440 to 1300 Ma ages are related to fault reactivation and a thermal pulse at similar to 1440 to 1400 Ma possibly accompanied by fluid flow, with subsequent enhanced cooling possibly due to thermal relaxation or further crustal exhumation. The youngest thermal and/or fluid-flow event at 1250 to 1150 Ma is recorded mainly to the cast of the Tern-lite Range fault and may be related to the assembly of the Rodinian supercontinent. Fluids in equilibrium with illite that formed over a range of temperatures, at different times in different parts of the platform. have relatively uniform oxygen isotope compositions and more variable hydrogen isotope compositions (delta O-18 = 3.5-9.7 parts per thousand V-SMOW; delta D = -94 to -36 parts per thousand V-SMOW). The extent of the 180 enrichment and the variably depleted hydrogen isotope compositions suggest the illite interacted with deep-basin hypersaline brines that were composed of evaporated seawater and/or highly evolved meteoric water. Siderite is the most abundant iron-rich gangue phase in the Century Zn-Pb deposit, which is surrounded by all extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120 degrees to 150 degrees C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150 degrees to 180 degrees C. The calculated isotopic compositions of the fluids are consistent with O-18-rich basinal brines and mixed inorganic and organic carbon Sources (6180 = 3-10 parts per thousand V-SMOW, delta C-13 = -7 to -3 parts per thousand V-PDB). in the northeast Lawn Hill platform carbonate-rich rocks preserve marine to early diagenetic carbon and oxygen isotope compositions, whereas ferroan carbonate cements in siltstones and shales in the Desert Creek borehole are O-18 and C-13 depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160 degrees-270 degrees C) and inverse correlation with carbonate delta O-18 values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids. The calculated isotopic compositions of the fluid are consistent with evolved basinal brine (delta O-18 = 5.1-9.4 parts per thousand V-SMOW; delta C-13 = -13.2 to -3.7 parts per thousand V-PDB) that contained a variable organic carbon component from the oxidation and/or hydrolysis of organic matter in the host sequence. The occurrence of extensive O-18- and C-13-depleted ankerite and siderite alteration in Desert Creek is related to the high temperature of the 1250 to 1150 Ma fluid-flow event in the northeast Lawn Hill platform, in contrast to the lower temperature fluids associated with the earlier Century Zn-Pb deposit in the central Lawn Hill platform.

Structural studies in tellurium chemistry

The primary theme of this research was the characterisation of new and novel organo-tellurium complexes, using the technique of single crystal X-ray analysis to establish more firmly the various coordination modes of tellurium. In each study the unit cell dimensions and intensity data were collected using an Enraf-Nonius CAD-4, four circle diffractometer. The raw data collected in turn was transferred to the Birmingham University Honeywell Multics System and processed using the appropriate computer packages for the determination of crystal structures. The molecular and crystal structures of: bis[2-(2-pyridyl)phenyl]tritelluride, bis[2-(N-hydroxy)iminophenyl] ditelluride, 2-(2-pyridyl)phenyltellurium(IV) tribromide, (2-N,N-dimethylbenzylamine-C,N')tellurium(IV)tribromide, 2-dichloro(butyl)tellurobenzaldehyde, 2-dichlorobutotelluro-N-dimethylbenzyl ammonium chloride, dimethyldithiocarbamato[2-(2-pyridyl)phenyl]tellurium(II), dimethyldithiocarbamato[2-(2-quinolinyl)phenyl]tellurium(II) and para-ethoxypheny[2-(2-pyridyl)phenyl]telluride are described. In each structure, the Lewis acidity of tellurium appears to be satisfied by autocomplex formation, through short-range intramolecular secondary bonds between tellurium and an electron denoting species, (generally nitrogen in these structures) with long range weak inter molecular contacts forming in the majority of the tellurium(IV) structures. The order of Lewis acidity in each structure can be considered to be reflected by the length of the short range intramolecular secondary bond, identified, that is, when tellurium has a low Lewis acidity this interaction is long. Interestingly, no primary bonds are found trans to a Te-C covalent bond in any of the above structures, highlighting the strong trans effect of aromatic and aryl groups in tellurium complexes.

Studies in organobismuth chemistry

Perturbations in the bismuth market resulted in Mining and Chemical Products Ltd., seeking further outlets in the market. Together with Manchem Ltd. they were anxious to evaluate the possibility of using bismuth compounds as a replacement for lead/calcium soaps in paint driers. A range of new organobismuth compounds were synthesised of the type RBiX2 and R3BiX2 (X= halogen, OOCR, dithiocarbamate). A variety of synthetic techniques were explored, including the use of mathematical reactions, phase-transfer catalysis and microwave energy. The preparation of a range of trivalent and pentavalent organobismuth carboxylates is reported and their infra-red , 13C, lH nmr spectra. The compounds were evaluated as paint driers and in cases found to enhance paint drying to a greater degree than the standard driers, to which they were being compared. The drying times of paint films containing the organobismuth compounds are reported, together with a comparison of the drying times with the addition of bismuth tris-diethyldithiocarbamate, which may promote the cross-linking reaction that occur in paint films during the drying process. Examples are reported to illustrate the great reductions in reaction times possible when using microwave energy. Reactions such as metallation of aromatic rings, ligand redistribution and synthesis were carried out in PTFE containers in a conventional domestic microwave oven. An X-ray diffraction study of (phenylazophenyl-C,N')mercury(II) chloride has shown it to be dimeric via long Hg-Cl bridging interactions of 3.367A. Its crystal structure is reported, together with its 13C nmr spectra and mass spectrum. The Lewis acidity of compounds of the type RBiX2 was investigated. The donor group being anchored to the organo group (R). The dithiocarbamates bis- (diethyldithiobarbamato)phenylbismuth(Ill) and [2-2-pyridyl)phenylbismuth(III) were synthesised, and their crystal structures, 14N, 13C nmr ar1d infra-red spectra are reported. Both compounds are pseudo-pentagonal bipyramidal in geometry, with two long Bi-S bonds and two short Bi-S bonds. The reaction of RBiBr2 (R= 2-(pyridyl) with various ligands is reported. The infra-red evidence suggesting that the coordination of extra ligands is accompanied by a reduction of the strength of the Bi-interaction.