Metal–organic complexation in the marine environment

We discuss the voltammetric methods that are used to assess metal–organic complexation in seawater. These consist of titration methods using anodic stripping voltammetry (ASV) and cathodic stripping voltammetry competitive ligand experiments (CSV-CLE). These approaches and a kinetic approach using CSV-CLE give similar information on the amount of excess ligand to metal in a sample and the conditional metal ligand stability constant for the excess ligand bound to the metal. CSV-CLE data using different ligands to measure Fe(III) organic complexes are similar. All these methods give conditional stability constants for which the side reaction coefficient for the metal can be corrected but not that for the ligand. Another approach, pseudovoltammetry, provides information on the actual metal–ligand complex(es) in a sample by doing ASV experiments where the deposition potential is varied more negatively in order to destroy the metal–ligand complex. This latter approach gives concentration information on each actual ligand bound to the metal as well as the thermodynamic stability constant of each complex in solution when compared to known metal–ligand complexes. In this case the side reaction coefficients for the metal and ligand are corrected. Thus, this method may not give identical information to the titration methods because the excess ligand in the sample may not be identical to some of the actual ligands binding the metal in the sample.     

Barium isotopes in individual presolar silicon carbide grains from the Murchison meteorite

Barium isotopic compositions of single 2.3-5.3 μm presolar SiC grains from the Murchison meteorite were measured by resonant ionization mass spectrometry. Mainstream SiC grains are enriched in s-process barium and show a spread in isotopic composition from solar to dominantly s-process. In the relatively coarse grain size fraction analyzed, there are large grain-to-grain variations of barium isotopic composition. Comparison of single grain data with models of nucleosynthesis in asymptotic giant branch (AGB) stars indicates that the grains most likely come from low mass carbon-rich AGB stars (1.5 to 3 solar masses) of about solar metallicity and with approximately solar initial proportions of r- and s-process isotopes. Measurements of single grains imply a wide variety of neutron-to-seed ratios, in agreement with previous measurements of strontium, zirconium and molybdenum isotopic compositions of single presolar SiC grains.     

Degassing and differentiation in subglacial volcanoes, Iceland

Within the neovolcanic zones of Iceland many volcanoes grew upward through icecaps that have subsequently melted. These steep-walled and flat-topped basaltic subglacial volcanoes, called tuyas, are composed of a lower sequence of subaqueously erupted, pillowed lavas overlain by breccias and hyaloclastites produced by phreatomagmatic explosions in shallow water, capped by a subaerially erupted lava plateau. Glass and whole-rock analyses of samples collected from six tuyas indicate systematic variations in major elements showing that the individual volcanoes are monogenetic, and that commonly the tholeiitic magmas differentiated and became more evolved through the course of the eruption that built the tuya. At Herdubreid, the most extensively studies tuya, the upward change in composition indicates that more than 50 wt.% of the first erupted lavas need crystallize over a range of 60°C to produce the last erupted lavas. The S content of glass commonly decreases upward in the tuyas from an average of about 0.08 wt.% at the base to < 0.02 wt.% in the subaerially erupted lava at the top, and is a measure of the depth of water (or ice) above the eruptive vent. The extensive subsurface crystallization that generates the more evolved, lower-temperature melts during the growth of the tuyas, apparently results from cooling and degassing of magma contained in shallow magma chambers and feeders beneath the volcanoes. Cooling may result from percolation of meltwater down cracks, vaporization, and cycling in a hydrothermal circulation. Degassing occurs when progressively lower pressure eruption (as the volcanic vent grows above the ice/water surface) lowers the volatile vapour pressure of subsurface melt, thus elevating the temperature of the liquidus and hastening liquid-crystal differentiation.     

A 29Si NMR study of silica species in dilute aqueous solution

The speciation of silica in dilute, nearly neutral, aqueous solution has been determined by ²⁹Si NMR. Our results indicate that tetrahedral dimers in addition to monomers occur in the concentration range of dissolved amorphous silica.     

Isotopic anomalies in meteorites and their origins—V. Search for fission fragment recoils in Allende sulfides

Three troilite- and pentlandite-rich samples from the Allende C3 chondrite were analyzed for Xe (and in one case Ne and Ar) by mass spectrometry, in 13–22 temperature steps. All samples released a small ‘CCFXe’ component (enriched in the heavy isotopes Xe^{134, 136}) at the relatively low temperature of 700–800°C, ahead of adsorbed atmospheric Xe (~900°C), radiogenic Xe¹²⁹ (1000°C), and primordial Xe (1250°C). Though such a labile component suggests implanted fission recoils, the simultaneous release of Ne, Ar, and Xe^{124, 126} shows that it instead comes from carbon and perhaps chromite, two major host phases of CCFXe. Apparently small amounts of these phases are occluded in sulfides, and decompose by chemical reaction upon heating. Thus the experiment fails to resolve the nature of CCFXe.A marked enrichment of Xe¹²⁴, without corresponding enrichments in Xe¹²⁶ or Xe^131–136, was observed in the 550–650° and 1400–1500° fractions. Though requiring confirmation, it supports earlier evidence for the complexity and variability of the light xenon component, contrary to claims that it is an integral part of CCFXe.     

Controls on the stability of sulfide sols: Colloidal covellite as an example

The conditions under which dilute CuS sols might be stable in natural waters have been explored. In single electrolyte solutions at room temperature, coagulation data adhere approximately to the classic theory for electrostatic stabilization. From this theory, the Hamaker constant is estimated to be 4 × 10^?19J. In a simple, four-component, synthetic seawater, coagulation occurs at 0.14 g/kg salinity. The critical coagulation concentration for CaCl₂ drops by a factor of six between 25 and 175°C. These measurements, which appear to be the first over so large a temperature range, confirm previous suppositions about the effect of temperature. The results suggest that electrostatic stabilization will be ineffective in nature for substances like CuS with large Hamaker constants, because divalent cation concentrations in most aquatic environments are sufficient for coagulation. Three alternate mechanisms by which organic compounds can stabilize sulfide sols are reported: chelation of counterions. surface hydrophillization through adsorption, and steric stabilization by polymers. Humic acid, which contributes stability when present at less than 1 mg C/1, may stabilize by all three mechanisms. However, theory indicates that even in the absence of chemical stabilization, extremely dilute sols such as would be encountered in anoxic marine basins might require many years to coagulate, thus appearing stable even if not.     

A carbonaceous inclusion from the Krymka LL-chondrite: noble gases and trace elements

A black inclusion from the Krymka LL3 chondrite was analyzed for 20 trace elements and five noble gases, by radiochemical neutron activation and mass spectrometry. The trace element pattern somewhat resembles that of C1 or C2 chondrites, but with several unique features. Elements of nebular condensation T ? 1000 K (U, Re, Os, Ir, Ni, Pd, Au, Sb and Ge) are essentially undepleted, as in C1 chondrites, but $\text{Re}\text{Ir}$ is 1.49 × higher than the characteristic Cl value. Among elements condensing below 1000 K, Cs, Se, Te, and In are depleted to approximately C2 levels (~0.6 × C1), whereas Ag, Bi, Tl are enriched to ~ 1.6 × C1. Such enrichments are thought to be characteristic of late nebular condensates.The noble-gas pattern also is unique. Gas contents are higher than in C1s, by factors of 2.6 to 19 for Ne through Xe. The $\text{Ar}{}^{36}\text{Xe}{}^{132}$ ratio of 500 is higher than mean values for C1s or C2s (109 or 89) and exceeds even the highest value seen in C3Os, 420, whereas the $\text{He}{}^4\text{Ne}{}^{20}$ ratio of 62 is much lower than the values for C1s and C2s (200–370). The $\text{Xe}{}^{129}\text{Xe}{}^{132}$ and $\text{Xe}{}^{136}\text{Xe}{}^{\mathrm{l32}}$ ratios of 1.040 and 0.320 resemble those of C1 chondrites, and seem to imply typical proportions of radiogenic Xe¹²⁹ and ‘fissiogenic’ xenon.It appears that the inclusion represents a new primitive meteorite type, similar to C-chondrites, but probably a late condensate from a region of higher nebular pressure.