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A.H. Truesdell

Publications and source records attributed to A.H. Truesdell.

33 records · Page 2Linked to original sources

Techniques for the conversion to carbon dioxide of oxygen from dissolved sulfate in thermal waters

The fractionation of oxygen isotopes between dissolved sulfate ions and water provides a useful geothermometer for geothermal waters. The oxygen isotope composition of dissolved sulfate may also be used to indicate the source of the sulfate and processes of formation. The methods described here for separation, purification and reduction of sulfate to prepare carbon dioxide for mass spectrometric analysis are modifications of methods by Rafter (1967), Mizutani (1971), Sakai and Krouse (1971), and Mizutani and Rafter (1969). ?? 1976.

Geothermics

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275°C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO 2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl 2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (10 3 ln α) between 1 molal solutions and pure water at 25, 100, and 275°C are: NaCl 0.0, −1.5, +1.0; KCl 0.0, −1.0, +2.0; LiCl −1.0, −0.6, −0.5; CaCl 2 −0.4, −1.8, +0.8; MgCl 2 −1.1, −0.7, −0.3; MgSO 4 −1.1, +0.1, −; NaF (0.8 m) 0.0, −1.5, −0.3; and NH 4 Cl (0.55 m) 0.0, −1.2, −1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required.

Earth and Planetary Science Letters

An empirical NaKCa geothermometer for natural waters

An empirical method of estimating the last temperature of water-rock interaction has been devised. It is based upon molar Na, K and Ca concentrations in natural waters from temperature environments ranging from 4 to 340°C. The data for most geothermal waters cluster near a straight line when plotted as the function log ( Na K ) + β log [ √ (Ca) Na ] "> log (NaK) + β log [ √(Ca)Na] vs reciprocal of absolute temperature, where β is either 1 3 "> 13 or 4 3 "> 43 depending upon whether the water equilibrated above or below 100°C. For most waters tested, the method gives better results than the Na K "> NaK methods suggested by other workers. The ratio Na K "> NaK should not be used to estimate temperature if √ ( M Ca ) M Na "> √ (MCa)MNa is greater than 1. The Na K "> NaK values of such waters generally yield calculated temperatures much higher than the actual temperature at which water interacted with the rock. A comparison of the composition of boiling hot-spring water with that obtained from a nearby well (170°C) in Yellowstone Park shows that continued water-rock reactions may occur during ascent of water even though that ascent is so rapid that little or no heat is lost to the country rock, i.e. the water cools adiabatically. As a result of such continued reaction, waters which dissolve additional Ca as they ascend from the aquifer to the surface will yield estimated aquifer temperatures that are too low. On the other hand, waters initially having enough Ca to deposit calcium carbonate during ascent may yield estimated aquifer temperatures that are too high if aqueous Na and K are prevented from further reaction with country rock owing to armoring by calcite or silica minerals. The Na-K-Ca geothermometer is of particular interest to those prospecting for geothermal energy. The method also may be of use in interpreting compositions of fluid inclusions.

Wyoming

Ion association in natural brines

Natural brines, both surface and subsurface, are highly associated aqueous solutions. Ion complexes in brines may be ion pairs in which the cation remains fully hydrated and the bond between the ions is essentially electrostatic, or coordination complexes in which one or more of the hydration water molecules are replaced by covalent bonds to the anion. Except for Cl − , the major simple ions in natural brines form ion pairs; trace and minor metals in brines form mainly coordination complexes. Limitations of the Debye-Hückel relations for activity coefficients and lack of data on definition and stability of all associated species in concentrated solutions tend to produce underestimates of the degree of ion association, except where the brines contain a very high proportion of Cl − . Data and calculations on closed basin brines of highly varied composition have been coupled with electrode measurements of single-ion activities in an attempt to quantify the degree of ion association. Such data emphasize the role of magnesium complexes. Trace metal contents of closed basin brines are related to complexes formed with major anions. Alkaline sulfo- or chlorocarbonate brines (western Great Basin) carry significant trace metal contents apparently as hydroxides or hydroxy polyions. Neutral high chloride brines (Bonneville Basin) are generally deficient in trace metals. With a knowledge of the thermodynamic properties of a natural water, many possible reactions with other phases (solids, gases, other liquids) may be predicted. A knowledge of these reactions is particularly important in the study of natural brines which may be saturated with many solid phases (silicates, carbonates, sulfates, etc.), which may have a high pH and bring about dissolution of other phases (silica, amphoteric hydroxides, CO 2 , etc.), and which because of their high density may form relatively stable interfaces with dilute waters.

Chemical Geology

Interstitial brines in playa sediments

Study of several closed drainages in the Great Basin has shown that the interstitial solutions of shallow, fine-grained playa deposits store a large quantity of dissolved solids and are often more concentrated than associated lakes and ponds, except in peripheral zones of stream or ground-water inflow. These interstitial fluids, when compared with local runoff, impoundments, or spring waters, commonly have a distinctive ionic composition which sometimes cannot be explained by either simple mixing of surface and subsurface inflow or by evaporative concentration. At Abert Lake, Oregon, the interstitial solute concentrations increased with depth to values as much as five times greater than the lake, except where springs indicate significant ground-water input. Where Na + , Cl, and CO 2 species constitute more than 90% of the solutes, Na + Cl − "> Na+Cl− ratios in the lake water are lower than in interstitial solutions of bottom cores and higher than in playa fluids. At the same time, Na + K + "> Na+K+ ratios are highest in the fluids of lake bottom muds and lowest in playa interstitials. In deeper playa profiles, interstitial Na + Cl − "> Na+Cl− tended to decrease with depth (5 ft. maximum). In the Abert Lake area, as in other parts of the western Great Basin, Na + Cl − "> Na+Cl− ratios are indicative of total CO 2 in solution and the effects of organic decay in surficial sediments. These ratios, coupled with data on silica and bulk density, show that higher P CO2 accompanying decay promotes silicate dissolution and hydrogen ion exchange, stripping alkalis from sediment which had preferentially adsorbed K + when entering the lake. On subsequent loss of pore fluid in the playa regime, silica initially released to solution in the lake environment is readsorbed on dissolution products.

Oregon

Dissociation constants of KSO 4 - from 10°-50°C

A cell without liquid junction was used to obtain dissociation constants for the reaction: KSO 4 − = K + + SO 4 2− . At 10°, 25°, 38° and 50°C, values for K diss KSO 4 − are, respectively, 0.19 5 , 0.14 2 , 0.11 7 , and 0.09 5 . At 25°C, , and values for the KSO 4 − ion are −245.96 and −274.02 kcal mole −1 , and S ° is +42.3 cal mole −1 deg −1 .

Geochimica et Cosmochimica Acta

Glass electrode determination of sodium in closed basin waters

Because of its direct relation to total dissolved solids content, sodium concentration is the most useful single hydrochemical parameter of closed basin waters in the western United States. Therefore, it is advantageous to have a rapid method for sodium determination which could be readily adapted to field use. Accordingly, thirty waters of highly variable concentration and anionic composition from the western Great Basin have been analyzed with a sodium-sensitive glass electrode. Na + values ranged from 10 to 130,000 ppm in waters containing from 102 to 401,000 ppm total dissolved solids. The electrode values were compared with conventional sodium determinations; results differed by as much as 11 per cent, although over two-thirds were within 5 per cent. No significant relation was found between the glass electrode and conventional method differences and the total dissolved solids or sodium concentration. The comparative accuracy of electrode and conventional procedures was checked, employing solutions of known sodium concentration. It was concluded that for the analysis of sodium in natural waters the glass electrode method offers results comparable in accuracy to those obtained by conventional methods, but with increased simplicity, and therefore the possibility of rapid, accurate field measurements.

Geochimica et Cosmochimica Acta

Phosphate glass electrode with good selectivity for alkaline-earth cations

A phosphate glass has been found to have a significant electrode specificity toward alkaline-earth ions. The order of selectivity is 2H + > Ba ++ > Sr ++ > Ca ++ > 2K + > 2Na + > Mg ++ . Exchange properties are discussed in relation to possible structure. Its use to determine activity of Ca ++ in natural systems containing Mg ++ is suggested.

Science

Study of natural glasses through their behaviour as membrane electrodes

THE low-temperature chemical alteration of natural glass occurs in two stages: an initial stage in which it remains glassy but absorbs as much as 6 per cent water 1 , and a final stage in which devitrification to clay minerals, with release of silica, occurs 2,3 . During the first stage the composition of the glass may change, with gain of K 2 O and water and loss of Na 2 O (Smith, R. L., personal communication). This change is due to ion exchange.

Nature

Glass electrodes sensitive to divalent cations

Glass electrodes suitable for measurement of divalent cations have been made and tested. Empirical and theoretical electrode equations have been presented to describe electrode behavior in a variety of aqueous solutions. Most electrodes show response interpretable as showing nearly ideal solid-solution behavior of the cations in the glass surface. The electrodes should be useful in the measurement of divalent-cation activities in natural waters and biological fluids, and useful in general analytical chemistry.

Science