Application of the 227Th230Th method to dating Pleistocene carbonates and comparison with other dating methods

The ${}^{227}\text{Th}{}^{230}\text{Th}$ dating method is described in detail and its usefulness investigated by comparing ages of sixteen Pleistocene carbonates (mainly cave deposits) with those determined by the ${}^{231}\text{Pa}{}^{235}\text{U}$ and ${}^{230}\text{Th}{}^{234}\text{U}$ methods. The ${}^{227}\text{Th}{}^{230}\text{Th}$ ages are found to be critically dependent on corrections for decay of ²²⁷Th prior to alpha counting and ingrowth of daughter isotopes of ²³²Th derived from clastic detritus. Of nineteen sets of ages determined for the sixteen samples, good agreement is found for only seven sets. Differences are attributed to low U content of some samples and the possibility of excess ²²⁷Th in the calcite of samples younger than ~50 ky, possibly due to the coprecipitation of ²³¹Pa during formation. Calculated “negative” ${}^{227}\text{Th}{}^{230}\text{Th}$ ages may be a direct result of this process and the fact that, unlike the other methods, the activity ratio is non-zero at zero age. Nevertheless, the ${}^{227}\text{Th}{}^{230}\text{Th}$ is found to be a useful alternative dating technique for carbonates which are between ~50 and 300 ky, because no spiking is required. It also serves as a check for partial concordancy with ages dated by the other methods.     

Uranium-series dating of lacustrine limestones from pan deposits with final Acheulian assemblage at Rooidam,Kimberley district,South Africa

Lacustrine limestone samples from sedimentary pan deposits at Rooidam, near Kimberley, South Africa, that contain late Acheulian (Fauresmith) artifacts have been dated by ${}^{230}\text{Th}{}^{234}\text{U}$ and ${}^{231}\text{Pa}{}^{235}\text{U}$ methods. Results indicate a minimum age of about 200,000 yr B.P. for the terminal Acheulian in the interior of South Africa.     

Comparison of 230Th-238U disequilibrium systematics in lavas from three hot spot regions: Hawaii,Prince Edward and Samoa

²³⁰Th-²³⁸U disequilibrium systematics reveal several important characteristics of the mantle source regions and petrogenesis of volcanic rocks in the presumed hot spots of Hawaii, Marion Island (Prince Edward hot spot), and Samoa. The (${}^{230}\text{Th}{}^{232}\text{Th}$) activity ratios of lavas from these three hot spots (1.06 ± 0.07, 1.04 ± 0.08, and 0.81 ± 0.06, respectively) imply that the source regions are each nearly homogeneous with $\text{Th}\text{U}$ weight ratios of 2.9, 3.0, and 3.8. For Marion Island and Mauna Kea, Hawaii, negligible secular variation occurs in the (${}^{230}\text{Th}{}^{232}\text{Th}$) initial ratios. This supports other evidence for very short transfer time between source and surface. Significant residence time at depth prior to eruption cannot be ruled out for the Samoan lavas we have studied; however, the data for one of these flows deviate from the proposed (${}^{230}\text{Th}{}^{232}\text{Th}$)-${}^{87}\text{Sr}{}^{86}\text{Sr}$ correlation (Condomineset al., 1981a) in the opposite sense from that expected for such residence. If it is assumed that the measured (${}^{230}\text{Th}{}^{232}\text{Th}$) ratios of the young lavas reflect $\text{Th}\text{U}$ in their mantle sources, then the observed variations among these three hot spots, combined with those reported by other workers for Iceland, the Azores and Tristan de Cunha, suggest that these sources are characterized by $\text{Th}\text{U}$ ratios ranging from values similar to that of MORB source (~2.5) to values similar to those of bulk earth (~3.8). Mixing of different proportions of depleted and enriched mantle may be responsible for the observed range.     

Thorium and radium isotopic relationships in manganese nodules and sediments at MANOP Site S

Relationships among Th and Ra isotopes in nodule, sediment and water phases at MANOP Site S establish the most likely source for Th in the nodules, the frequency of nodule turning, and the similarity of micro and macro nodules. Manganese nodules and bottom waters have ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios considerably higher than other phases at this site suggesting that sea water is the likely source of Th for the nodules. Similar ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios in nodule tops and bottoms and in certain cases departure from expected ${}^{226}\text{Ra}{}^{230}\text{Th}$ activity ratios in nodule tops and bottoms indicate that the nodules rotate every one to ten thousand years. The micro nodules have diffusion coefficients of Ra similar to macro nodule bottoms. I suggest that they may act as a carrier phase for transporting metals through oxic sediments to nodules.     

Redistribution of uranium and thorium series isotopes during isovolumetric weathering of granite

Previous studies of the distribution of U and Th in parent versus weathered granites have shown both depletion and enrichment of these elements during weathering. In this study, the distribution of U and Th decay series isotopes was determined in a weathering profile of a granitic saprolite, which showed textural preservation indicating isovolumetric weathering. Two types of dissolution methods were used: a whole-rock dissolution and a sodium-citrate dithionite leach to preferentially attack noncrystalline phases of weathering products. Using volume-based activities, 45–70 percent of the total ²³²Th was gradually removed during weathering. Although the whole-rock ${}^{228}\text{Th}{}^{232}\text{Th}$ activity ratios were in equilibrium, there were large excesses of ²²⁸Th in the leachable fraction of both parent rock (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 2.06}$) and partially weathered saprolite (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 3–6.5}$), due to alpha recoil and release of daughter ²²⁸Th to the weathering rind of the mineral grain. For the most weathered sample, 81 percent of the thorium was in the teachable fraction and ${}^{228}\text{Th}{}^{232}\text{Th}\text{= 1}$, indicating that even the more resistant minerals were attacked.The total U activities showed as much variation in the six parent rock samples as in the weathered profile, and ${}^{234}\text{U}{}^{238}\text{U}$ were in equilibrium in both the whole-rock and leachable fractions. ²³⁰Th was deficient relative to ²³⁴U and ²²⁶Ra in both fractions, suggesting recent addition of U and Ra to the entire profile. The large variation in U was not from absorption onto the intermediate weathering products, because only 11–23 percent of the U was in the leachable fraction.     

Growth of a manganese nodule from Peru Basin: A radiochemical anatomy

Attempts have been made to study the entire growth history of a manganese nodule from the northern part of Peru Basin in the Pacific using radiochemical profiles of ${}^{230}\text{Th}{}^{232}\text{Th}$, ${}^{227}\text{Th}{}^{230}\text{Th}$, and ${}^{10}\text{Be}{}^9\text{Be}$. Combined with the observations on Fe-Mn contents and textural variation, the radiochemical data indicate that the nodule grew more or less concentrically throughout most of its existence since it formed 1.5 my ago, receiving Mn from both bottom water and pore water. This condition appeared to have changed about 180 ky ago when the growth became asymmetric in that the top and bottom sides became fixed in their relative positions on the sea floor. Since then, the bottom side accreted with a fast rate of close to 200 mm/my, apparently fueled by the supply of diagenetically remobilized Mn in pore water from the sediment substrate. In the meantime, the top side accumulated at about 6 mm/my, a value which is in the normal range for deep-sea nodules having their Mn supplied from the hydrogenous source.     

Glacial to interglacial changes in carbonate and clay sedimentation in the Atlantic Ocean estimated from 230Th measurements

The cause of the climatically controlled fluctuations in the carbonate content of deep-sea sediments remains the subject of uncertainty and debate. Three variables are involved: supply of biogenic carbonate, loss by dissolution, and dilution by non-carbonate phases. It is suggested that ²³⁰Th, which is produced in the ocean at a constant rate provides a reliable reference for measuring variations in rate of sedimentation on a regional scale. Results of a preliminary analysis based on published data indicate that, for depths at and above the lysocline, the carbonate fluctuations observed in cores from the North Atlantic Ocean are due primarily to variations in the terrigenous clay input, which was 2–5 times higher during glacials than during interglacials. Carbonate deposition appears to have been somewhat reduced during glacials, but probably not by more than a factor of 2. From published ${}^{230}\text{Th}{}^{232}\text{Th}$ profiles it appears that the South Atlantic Ocean also received increased inputs of terrigenous clay during glacial periods.     

Late Pleistocene paleoclimates of North America as inferred from stable isotope studies of speleothems

Some speleothems (CaCO₃ cave deposits) can be demonstrated to have been formed in oxygen isotopic equilibrium with their parent seepage waters and thus a record of relative fluctuations in depositional temperature can be obtained from the δ¹⁸O variations in successive growth layers of such deposits. These temperature fluctuations reflect variations in the average annual air temperature at the surface above the cave, and therefore permit inference of past continental climate changes. Equilibrium deposits have been obtained from caves in San Luis Potosi, Bermuda, Kentucky, West Virginia, Iowa, and Alberta, ranging in age from 200,000 years BP to the present, as determined by ${}^{230}\text{Th}{}^{234}\text{>U}$ dating of the speleothems. The δ¹⁸O time curves for the six sites show the following synchronous climatic fluctuations: warm periods from 190 to 165 and from 120 to 100 Ka, at 60 and 10 Ka, and cold periods from 95 to 65 and from 55 to 20 Ka. The periods of thermal maxima correspond in time to the interglacial periods of the marine foraminiferal isotopic and faunal temperature records and to periods of high sea stand as observed from radiometric dating of raised coral reefs. Maxima and minima in insolation appear to be synchronous with this record as well.     

The solubilities of calcite,aragonite and vaterite in CO2-H2O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.     

Magmatic evolution of a volcano studied by 230Th-238U disequilibrium and trace elements systematics: The Etna case

Age determinations of several lava flows from Etna through ²³⁰Th-²³⁸U disequilibrium (internal isochrons) yield a precise chronology of the volcano's history for the last 200,000 years, and emphasize the main episodes in the formation of this huge complex strato-volcano. Study of $\text{(}{}^{230}\text{Th}{}^{232}\text{Th}\text{)}{}_0$ initial ratios of lavas together with their trace-element compositions yields a consistent model of magmatic evolution implying the existence, for 200,000 years, of a deep reservoir of alkalic magma periodically mixed with magmas of tholeiitic affinity. These short periods of mixing appear to be related to the formation of the large calderas of Etna. In addition to these processes affecting the deep reservoir, fractional crystallization also occurred in more superficial levels of the volcanic edifice, thereby yielding several series of differentiation of relatively short duration. As for its geochemistry, Etna's volcanism is of oceanic type but with its own characteristics and in a peculiar geodynamic context, at the edge of the African Plate.     

Liquidus relationships in the system CaCO3Ca(OH)2CaS and the solubility of sulfur in carbonatite magmas

CaCO₃Ca(OH)₂CaS serves as a model system for sulfide solubility in carbonatite magmas. Experiments at 1 kbar delineate fields for primary crystallization of CaCO₃, Ca(OH)₂ and CaS. The three fields meet at a ternary eutectic at 652°C with liquid composition (wt%): CaCO₃ = 46.1%, Ca(OH)₂ = 51.9%, CaS = 2.0%. Two crystallization sequences are possible for liquids that precipitate calcite, depending upon whether the liquid is on the low-CaS side, or the high-CaS side of the line connecting CaCO₃ to the eutectic liquid. Low-CaS liquids precipitate no sulfide until the eutectic temperature is reached leading to sulfide enrichment. The higher-CaS liquids precipitate some sulfide above the eutectic temperature, but the sulfide content of the melt is not greatly depleted as the eutectic temperature is approached. Theoretical considerations indicate that sulfide solubility in carbonate melts will be directly proportional to and inversely proportional to ; it also is likely to be directly proportional to melt basicity, defined here by . A strong similarity exists in the processes which control sulfide solubility in carbonate and in silicate melts. By analogy with silicates, ferrous iron, which was absent in our experiments, may also exert an important influence on sulfide solubility in natural carbonatite magmas.     

The formation of caliche in soils of the Mojave Desert,California

Radiocarbon and ²³⁰Th-²³⁴U dates of calcic horizons from calciorthid soil profiles in the Mojave Desert were used to calculate the rate of deposition of pedogenic CaCO₃. A major period of CaCO₃ deposition appears to have occurred about 20000 yBP forming calcic horizons below 100-cm depth during a climatic regime with greater effective rainfall than in the present. The overall rate of deposition has been 1.0 to 3.5 g CaCO₃/m²/yr during soil formation. This rate is consistent with present-day rates, assuming that the atmospheric deposition of Ca limits the process. Stable isotope ratios in calcic horizons indicate that CaCO₃ precipitated from a soil environment with CO₂ of ? 15.5%. ${}^{13}\text{C}{}^{12}\text{C}$ (vs. PDB) and H₂O of + 2.0%. ${}^{18}\text{O}{}^{16}\text{O}$ (vs. SMOW). These values suggest that CaCO₃ precipitates when seasonal drought simultaneously lowers soil pore pCO₂ and enriches soil water ¹⁸O by evaporation. The role of soil calcic horizons in the global geochemical cycle of carbon is discussed.     

Thermochemistry of the high structural state plagioclases

The enthalpies of solution of a suite of 19 high-structural state synthetic plagioclases were measured in a Pb₂B₂O₅ melt at 970 K. The samples were crystallized from analyzed glasses at 1200°C and 20 kbar pressure in a piston-cylinder apparatus. A number of runs were also made on Amelia albite and Amelia albite synthetically disordered at 1050–1080°C and one bar for one month and at 1200°C and 20 kbar for 10 hr. The component oxides of anorthite, CaO, Al₂O₃ and SiO₂, were remeasured.The ΔH of disorder of albite inferred in the present study from albite crystallized from glass is 3.23 kcal, which agrees with the 3.4 found by Holm and Kleppa (1968). It is not certain whether this value includes the ΔH of a reversible displacive transition to monoclinic symmetry, as suggested by Helgesonet al. (1978) for the Holm-Kleppa results. The enthalpy of solution value for albite accepted for the solid solution series is based on the heat-treated Amelia albite and is 2.86 kcal less than for untreated Amelia albite.The enthalpy of formation from the oxides at 970 K of synthetic anorthite is ?24.06 ± 0.31 kcal, significantly higher than the ?23.16 kcal found by Charluet al. (1978), and in good agreement with the value of ?23.89 ± 0.82 given by Robieet al. (1979), based on acid calorimetry.The excess enthalpy of mixing in high plagioclase can be represented by the expression, valid at 970 K: ΔH^ex(±0.16 kcal) = 6.7461 X_abX²_An + 2.0247 X_AnX²_Ab where X_Ab and X_An are, respectively, the mole fractions of NaAlSi₃O₈ and CaAl₂Si₂O₈. This ΔH^ex, together with the mixing entropy of Kerrick and Darken's (1975) Al-avoidance model, reproduces almost perfectly the free energy of mixing found by Orville (1972) in aqueous cation-exchange experiments at 700°C. It is likely that Al-avoidance is the significant stabilizing factor in the high plagioclase series, at least for X_An≥ 0.3. At high temperatures the plagioclases have nearly the free energies of ideal one-site solid solutions. The Al-avoidance model leads to the following Gibbs energy of mixing for the high plagioclase series: $\text{ΔG}{}^{\mathrm{mix}}\text{= ΔH}{}^{\mathrm{ex}}\text{+ RT X}{}_{\mathrm{Ab}}\text{ln[X}{}^2{}_{\mathrm{Ab}}\text{(2 ? X}{}_{\mathrm{Ab}}\text{)]+ X}{}_{\mathrm{An}}\text{ln}\text{[X}{}_{\mathrm{An}}\text{(1+X}{}_{\mathrm{An}}\text{)}{}^2\text{]}\text{4}$. The entropy and enthalpy of mixing should be very nearly independent of temperature because of the unlikelihood of excess heat capacity in the albite-anorthite join.     

Titan-aegirine from early Tertiary ash layers in northern Denmark

Microprobe analyses on a xenocrystic suite of salites, aegirine-augites, aegirines, titan-aegirines and acmites from a lower Tertiary ash layer in northern Denmark are presented. The sodic pyroxenes show an unusual titan-enrichment and up to 42 mol.% of the component $\text{NaTi}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^{\mathrm{4+}}\text{M}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^{\mathrm{2+}}\text{Si}{}_3\text{O}{}_6\text{(}\text{M = Fe}{}^{\mathrm{2+}}\text{,}\text{Mn or Mg}\text{)}$, is estimated. Optical absorption measurements show no evidence for Ti³⁺. The titan-aegirines were formed during late to post-magmatic crystallization in a system with a high Ti⁴⁺/Fe²⁺ ratio and were followed by acmite showing enrichment in jadeite. Comparison with experimentally investigated titan-aegirine indicates crystallization far below the Mn₂O₃Mn₃O₄f₀₂ buffer.     

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

Dissociation constants for alkali earth and sodium borate ion pairs from 10 to 50°C

Potentiometric measurements in dilute sodium borate solutions with added alkali earth chlordie salts yield the following expressions for the dissociation constants of alkali earth borate ion pairs from 10 to 50°C:

$\text{p}\text{K(}\text{MgH}{}_2\text{BO}{}_3{}^{\mathrm{+}}\text{=1.266+0.001204 T}$

$\text{p}\text{K(}\text{CaH}{}_2\text{BO}{}_3{}^{\mathrm{+}}\text{=1.154+0.002170 T}$

$\text{p}\text{K(}\text{SrH}{}_2\text{BO}{}_3{}^{\mathrm{+}}\text{=1.033+0.001738 T}$

$\text{p}\text{K(}\text{BaH}{}_2\text{BO}{}_3{}^{\mathrm{+}}\text{=1.942+0.001850 T}$

where T is in °K. Enthalpies for the dissociation reactions at 25°C are less than 1 kcal./mole for all the alkali earth borate ion pairs.Values for pK(NaH₂BO₃°) from 5 to 55°C computed from the experimental data of Owen and King are in good agreement with those determined potentiometrically. The average value from both methods is 0.22 ± 0.1 at 25°C.Application to seawater of computed pK's for MgH₂BO₃⁺, CaH₂BO₃⁺ and NaH₂BO₃⁰ yields an apparent dissociation constant for boric acid of 8.73 vs. 8.70 measured by Lyman, 8.68 by Buch and 8.73 by Byrne and Kester.     

The distribution of divalent trace elements between sulfides,oxides, silicates and hydrothermal solutions: I. Thermodynamic basis

Experimental data for the standard Gibbs free energies of formation from the elements of a wide variety of metal sulfides and oxides, spinels, olivines and pyroxenes at 25°C and 1 bar define linear correlations, within about ±900 cal·mole^?1, with the corresponding conventional standard partial molal Gibbs free energies of formation of the aqueous M²⁺ cations of the form where a_MaZ and b_MaZ are empirically determined constants characteristic of the structure M_nZ. The only exceptions to correlations of this type are compounds of the heavy alkaline earths Ca, Sr and Ba, which appear to follow correlations with cation radius instead. The linear free energy correlations enable prediction of standard Gibbs free energies of formation of compositional end-members of a particular structure M_nZ provided that a_MaZ and b_MaZ are known accurately. When only the free energy of the Mg end-member is known, the standard Gibbs free energy of formation at 25°C and 1 bar of the Fe endmember, and hence a_MaZ and b_MaZ Can be predicted from the temperature independence of and estimated entropies and heat capacities for the Fe end-member. Using this approach, the free energies of ferrosilite, hedenbergite and annite at 25°C and 1 bar were predicted to within ±1000 cal·mole^?1 of the helgesonet al. (1978) values. Free energies of formation of talc (M₃Si₄O₁₀(OH)₂), clinchlore (M₅Al₂Si₃O₁₀(OH)₈), and tremolite (Ca₂M₅(Si₄O₁₁)₂(OH)₂)-type compounds where M is Mg, Mn, Zn, Fe, Co, or Ni were then predicted at 25°C and 1 bar.Calculation of the equilibrium distribution of Mg, Zn and Sr between galena and hydrothermal solution, and Zn, Mg, Fe and Mn between chlorite and hydrothermal solution demonstrates: (1) that the Sr contents of low temperature galenas (e.g. Mississippi Valley-type) should be negligible (reported analyses of Sr content and Sr isotopic composition of such galenas are probably attributable to fluid inclusions or carbonate inclusions); and (2), that the Zn contents of hydrothermal chlorites in a model of the midoceanic ridge hydrothermal systems are sensitive to temperature, to complexing in the aqueous phase, and to the overall Fe/Mg ratio of the chlorite.