An evaluation of rate equations for calcite precipitation kinetics at pCO2 less than 0.01 atm and pH greater than 8

We used a reproducible seeded growth technique with a pH-stat to study the kinetics of calcite precipitation at 25°C. We performed different experiments at initial Ca²⁺ and HCO₃^? concentrations ranging from 0.7–2 and 4–7 mmol L^?1, pH values ranging from 8.25 to 8.70, $\text{pCO}{}_2$ values ranging from 0.0006 to 0.01 atm, and ionic strengths ranging from 0.015 to 0.10 mol L^?1. With this experimental data set, we used initial rate measurements and integral methods to test several precipitation rate equations. Rate equations that possess a disequilibrium functional dependence, such as the BURTON et al. (1951) dislocation model, forms of the Davies and Jones (1955) model, and the model used by Reddy and Nancollas (1973), did not adequately describe the kinetics of calcite precipitation at pH greater than 8 and $\text{pCO}{}_2$ less than 0.01 atm. Rate equations that describe independent dissolution and precipitation mechanisms with elementary reactions, such as the equation presented by Plummeret al. (1978), and nancollas and Reddy (1971) were more successful. However, Plummer's model did not adequately describe the rate of all experiments due to the presence of an OH^? surface term in the precipitation rate equation. The elementary reaction of the Nancollas and Reddy model is written in terms of bulk Ca²⁺ and CO₃^? concentrations, and appears to be the most successful model which describes calcite precipitation at pH > 8 and $\text{pCO}{}_2\text{< 0.01}$ atm. The Nancollas and Reddy model, altered to account for varying ionic strengths, adequately described the rate of all experiments and yielded a precipitation rate constant of $\text{118.2 ± 13.9}$ dm⁶ mol^?1 m^?2 s^?1, with an apparent Arrhenius activation energy of 48.1 kJ mol^?1.     

Isotope and trace element geochemistry of sediments from the Barbados Ridge-Demerara Plain region,Atlantic Ocean

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb${}^{206}\text{Pb}{}^{204}\text{Pb}$ up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and${}^{143}\text{Nd}{}^{144}\text{Nd}$ increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas.Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of “normal” depleted MORB.     

Copper(II) carbonate complexation in seawater

Cupric carbonate and cupric bicarbonate complexation constants were determined in natural seawater and in a variety of synthetic media. The formation constants of CuHCO₃⁺, CuCO₃⁰ and Cu(CO₃)₂^2? at 25°C and zero ionic strength are: log β_H⁰ = 1.8, log β₁⁰ = 6.82 and log β⁰₂ = 10.6. Formation constants of these species appropriate to 0.7 molar ionic strength and 25°C are log β_H ～- 1, log β₁ = 5.73, log β₂ = 9.3. Our results indicate that the inorganic speciation scheme of Cu(II) in seawater is dominated by CuCO₃⁰ and that the ternary species, CuCO₃OH^?, is of substantial importance.     

Late Holocene history of Waldsea Lake,Saskatchewan, Canada

The post-Hypsithermal history of Waldsea Lake, a saline meromictic lake located in south-central Saskatchewan, has been deduced from a study of the changes in physical, mineralogical, and paleobiological parameters in sediment cores from the basin. Six lithostratigraphic units and three palynological zones are identified in the most recent sediment. These units and zones indicate that a shallow hypersaline lake with extensive mudflats existed about 4000 yr B.P. In response to the subsequent trend toward a cooler and wetter climate, deeper water conditions ensued, and by about 3000 yr ago a relatively deep stratified lake occupied the Waldsea Basin. A short climatic reversal about 2500 yr B.P. again caused low-water and mudflat conditions, but by 2000 yr ago the lake had regained its higher levels. The past 2000 yr of Waldsea's history have been relatively uneventful, except for a minor lowering of the lake about 700 yr B.P.     

Instability model for recurring large and great earthquakes in southern California

The locked section of the San Andreas fault in southern California has experienced a number of large and great earthquakes in the past, and thus is expected to have more in the future. To estimate the location, time, and slip of the next few earthquakes, an earthquake instability model is formulated. The model is similar to one recently developed for moderate earthquakes on the San Andreas fault near Parkfield, California. In both models, unstable faulting (the earthquake analog) is caused by failure of all or part of a patch of brittle, strain-softening fault zone. In the present model the patch extends downward from the ground surface to about 12 km depth, and extends 500 km along strike from Parkfield to the Salton Sea. The variation of patch strength along strike is adjusted by trial until the computed sequence of instabilities matches the sequence of large and great earthquakes sincea.d. 1080 reported by Sieh and others. The last earthquake was theM=8.3 Ft. Tejon event in 1857. The resulting strength variation has five contiguous sections of alternately low and high strength. From north to south, the approximate locations of the sections are: (1) Parkfield to Bitterwater Valley, (2) Bitterwater Valley to Lake Hughes, (3) Lake Hughes to San Bernardino, (4) San Bernardino to Palm Springs, and (5) Palm Springs to the Salton Sea. Sections 1, 3, and 5 have strengths between 53 and 88 bars; sections 2 and 4 have strengths between 164 and 193 bars. Patch section ends and unstable rupture ends usually coincide, although one or more adjacent patch sections may fail unstably at once. The model predicts that the next sections of the fault to slip unstably will be 1, 3, and 5; the order and dates depend on the assumed length of an earthquake rupture in about 1700.     

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions. II. Rate constants,effective surface area,and the hydrolysis of feldspar

Analysis of experimental data reported by Lagache (1965, 1976), Evans (1965), Busenberg (1975), Busenberg and Clemency (1976), Holdren and Berner (1979), Siegel and Pfannkuch (1984), and Chou and Wollast (1984) with the aid of irreversible thermodynamics and transition state theory (Aagaard and Helgeson, 1977, 1982) suggests that at temperatures at least up to 650°C, the rate of both congruent and incongruent feldspar hydrolysis in aqueous solutions far from equilibrium at pH ? 10.6 ? (2300/T), where T stands for temperature in kelvins, is a function solely of effective surface area and pH at constant pressure and temperature. At higher pH, the rate is apparently pH-independent up to ~pH 8 at 25°C, where it again becomes pH-dependent at higher pH. Observations of scanning electron micrographs indicate that the cross-sectional area of etch pits on hydrolyzed feldspar grains is of the order of 10^?9 to 10^?8 cm² and that the ratio of the effective to total surface area (which may or may not change with reaction progress) ranges from <0.01 to 1, depending on the grain size, dislocation density, and the extent of comminution damage on the surfaces of the grains. Apparent rate constants retrieved from experimental data reported in the literature for feldspar hydrolysis in the lower pH-dependent range extend from ~10^?13 to ~10^?7 moles cm^?2 sec^?1 at temperatures from 25° to 200°C, which is consistent with activation enthalpies for albite and adularia of the order of 20 kcal mole^?1. In contrast, the apparent rate constants for the pH-independent rate law range from ~10^?16 to ~10^?11 moles cm^?2 sec^?1 at temperatures from 25° to 650°C, which requires an activation enthalpy for adularia of ~ 9 kcal mole^?1. These observations are consistent with surface control of reaction rates among minerals and aqueous solutions. The rate-limiting step in the pH-dependent case apparently corresponds at the lower end of the pH scale to breakdown of a protonated configuration of atoms on the surface of the reactant feldspar, but at higher pH the rate is limited by decomposition of an activated surface complex corresponding in stoichiometry to hydrous feldspar. In highly alkaline solutions, an activated complex containing hydroxyl ions apparently controls the rate of feldspar hydrolysis. Nevertheless, near equilibrium, regardless of pH the rate is proportional to the chemical affinity of the overall hydrolysis reaction.     

Geochemical constraints on magma processes in a peralkaline system: The Paisano volcano,west Texas

Major and trace element data for a sequence of peralkaline silicic lavas and pyroclastic flows, exposed in the caldera wall of the Paisano volcano, west Texas, document systematic fractional crystallization during magmatic evolution and an open system, magma mixing event in the upper parts of the sequence. Stratigraphically lowest flows are comendite and comenditic quartz trachyte lavas and ash flow tufts. Overlying these units is a trachyte with compositional, textural and mineralogical features indicating that it is the product of magma-mixing; similar flows occur in other parts of the volcano at the same stratigraphic level. This composite trachyte is considered to be a mixture of mugearitic or mafic trachytic magma, derived from a similar source region which yielded the earlier caldera wall flows. Trace element concentrations of the post-trachyte comenditic quartz trachyte lavas suggest they were erupted from a chamber whose magma was diluted by an influx of mugearitic or mafic trachytic magma during a magma mixing event.Rayleigh fractionation calculations show that the comendites and comenditic quartz trachytes can be derived from a parental mugearite magma by 88% to 93% fractionation of dominantly plagioclase and alkali feldspar, with lesser amounts of clinopyroxene, magnetite and apatite. Zircon was not a significant fractionating phase. The composition, mineralogy and depth of the source region(s) which generated these magmas cannot be constrained from the present data set.     

Occurrence and distribution of sulfur in peat-forming environments of southern Florida

Cores and surface samples of peats from the Everglades—Mangrove region of Southern Florida were analyzed for total sulfur and pyritic sulfur. These values were compared with the petrographic-botanical components of the peats as determined from point-counts of oriented microtome sections. Pyrite occurs as individual euhedral crystals, loosely packed framboids, and lenses or crusts of minute crystals. Framboids and minute crystals are often associated with organic matter and sometimes with bacteria and fungi. Pyrite tends to selectively occur in void spaces in or between peat tissues. In samples containing very small amounts of pyrite, framboidal pyrite is the prevalent form.Marine to brackish peats contain the highest pyrite and total sulfur contents, with brackish peats generally containing more pyrite than marine peats. Pyrite tends to be lower in all peats within 30 cm of the surface, whether marine or brackish.Burial of freshwater peats beneath marine or brackish peats tends to increase the total sulfur and pyritic sulfur in the underlying peats. Burial beneath brackish-water, clay-rich deposits (such as splays) tends to increase total sulfur and pyritic sulfur in the underlying deposits more than burial beneath less clay-rich deposits.     

Trace elements in rims and interiors of Chainpur chondrules

Trace elements were measured in the rims and interiors of nine chondrules separated from the Chainpur LL-3 chondrite. Whole rock samples of Chainpur and samples of separated rims were also measured. Chondrule rims are moderately enriched in siderophile and volatile elements relative to the chondrule interiors. The enriched volatile elements include the lithophilic volatile element Zn. The moderate enrichment of volatiles in chondrule rims and the lack of severe depletion in chondrules can account for the complete volatile inventory in Chainpur. These results support a three-component model of chondrite formation in which metal plus sulfide, chondrules plus rims and matrix silicates are mixed to form chondrites.