Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.     

Global tectonics of a despun planet

Mercury, the Moon, and many large satellites of the major planets have been tidally despun from an initially faster rotation. These bodies probably possessed equatorial bulges which relaxed as they lost their spin. An analysis of the stresses induced in an elastic shell by the relaxation of an equatorial bulge indicates that differential stresses may reach a few kilobars and that the tectonic pattern developed depends mainly upon the shell thickness. In every model studied the azimuthal stress σ_?? is larger (more compressive) than the meridional stress σθθ. For a thin elastic shell (thickness less than one-twentieth of the planet's radius) the zone from the equator to 48° latitude is characterized by strike-slip faulting. Poleward of this, normal faults and graben trending east-west are expected. Thicker elastic shells acquire an equatorial belt of thrust faults with east-west throw and rough north-south trends. These tectonic styles may be modified by a small (0.05-0.1%) radial expansion or contraction. Expansion shifts the polar normal faulting province toward the equator, while contraction shifts the equatorial provinces poleward. These patterns are not substantially altered by plastic yielding of the shell, although the equatorial thrust fault province is suppressed by strike-slip faulting until strike-slip faults occur poleward of 64.8° latitude. We conclude that there are many tectonic patterns consistent with despinning and radial contraction or expansion, but they must all be consistent with σ_?? > σθθ. These results also indicate that the polar regions of a despun planet are of particular interest in deciding whether a given lineament system is due to stresses induced by the relaxation of the planet's equatorial bulge.     

Magmatism in the eastern Aleutian Arc: temporal characteristic of igneous activity on Akutan Island

Lavas from Akutan Island, located in the eastern Aleutian arc at the transition between continental and oceanic crust, show a gradual change in their petrologic and chemical characteristics over the last 4 million years. The oldest lavas exposed on the island, the Hot Springs Bay Volcanics (HSBV), range from magnesian basalt to dacite (45%–62% SiO₂). The most mafic basalts contain salitic clinopyroxene, Cr- and Al-rich spinel, and pargasitic amphibole suggesting that they were derived from relatively hydrous magmas at greater pressures than lavas from the younger Akutan Volcanics (AKV) and the modern volcano (MOD). AKV lavas also range between basalt and dacite (46%–63% SiO₂), but contain no hydrous phenocrysts and seem to have fractionated within a shallow level magma chamber. Lavas from the modern volcano are andesitic (52%–57% SiO₂) and have a mineral assemblage similar to that of AKV lavas of similar composition. With the exception of clinopyroxene and spinel in the most mafic lavas, the compositions of plagioclase (An_92?45), olivine (Fo_88?51), orthopyroxene (En_69?56), and titanomagnetite (15%–21% TiO₂) phenocrysts found in these lavas are within the range observed in lavas from other Aleutian volcanoes. Variations in the major element chemistry of the older lavas can be reproduced by fractional crystallization of the observed mineral assemblages, however closed system crystal fractionation models are inadequate to explain the trace element variations. During the last 4 million years, La/Yb ratios have decreased (6.5–3.3 for HSBV lavas and 2.9–1.9 for MOD lavas) whereas Ba/La ratios appear to have increased slightly (37–43 for HSBV and AKV, and 41–45 of MOD). The lower La/Yb ratios of MOD lavas correspond with lower total abundances of the REE and slightly higher Sr and Pb isotopic ratios. The increased⁸⁷Sr/⁸⁶Sr ratios and Pb isotopic ratios in the MOD lavas, the less enriched LREE, and the higher Ba/La ratios may result from partial melting of an arc source which has experienced previous melting events but has continued to be contaminated by a component from the subducting slab. It may also indicate a change in the degree of partial melting of the underlying mantle, which corresponds to a different percentage of a slab derived component being incorporated into the overlying mantle.     

An experimental study of magnesium-isotope fractionation in chlorophyll-a photosynthesis

Measurements are presented of the magnesium isotopic composition of chlorophyll-a, extracted from cyanobacteria, relative to the isotopic composition of the culture medium in which the cyanobacteria were grown. Yields of 50-93% chlorophyll-a were achieved from the pigment extracts of Synechococcus elongatus, a unicellular cyanobacteria. This material was then digested using concentrated nitric acid to extract magnesium. Separation was accomplished using columns of cation-exchange resin, which achieved a 103 ± 10% yield of magnesium from chlorophyll-a. This procedure ensured accurate measurement of the magnesium-isotopic ratios without isobaric interferences using a multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We find a slight depletion in the heavier isotopes of magnesium in chlorophyll-a relative to culture medium, early growth phase: Δ²⁶Mg = −0.71(±0.35)‰ and Δ²⁵Mg = −0.37(±0.18)‰; late growth phase: Δ²⁶Mg = −0.53(±0.20)‰ and Δ²⁵Mg = −0.26(±0.11)‰, due to an apparent mass-dependent fractionation. We suggest that the small fractionation results from chelation during intracellular processes. A likely candidate for this chelation step involves the magnesium-chelatase enzyme, which mediates the insertion of magnesium to the tetrapyrrole ring during chlorophyll-a biosynthesis. Proof of this hypothesis can be tested with biological controls whereby steps in the enzymatic pathways of chlorophyll synthesis are selectively suppressed.     

Elasticity of tetragonal end-member majorite and solid solutions in the system Mg4Si4O12-Mg3Al2Si3O12

 The adiabatic elastic moduli of polycrystalline En₅₀Py₅₀ and En₈₀Py₂₀ majorite-garnet solid solutions (where En=4MgSiO₃, Py=Mg₃Al₂Si₃O₁₂) and the end-member En₁₀₀ tetragonal majorite were determined at ambient conditions using Brillouin spectroscopy. The adiabatic bulk modulus, K, and shear modulus, μ, of En₅₀Py₅₀ were found to be K=173.1 (20) and μ=92.3 (10) GPa, and are indistinguishable from those of the end-member pyrope, Py₁₀₀. The moduli of the more majorite-rich samples are significantly lower and are virtually identical to each other (K=162.6(11) and μ=85.7(7) for En₈₀Py₂₀; K=166(5) and μ=88(2) for En₁₀₀). In combination with previously reported moduli for this system, we conclude that both K and μ are constant over the compositional range from Py₁₀₀ to a majorite content of about 70–80%, whereupon the moduli decrease substantially. For compositions ranging from En₈₀Py₂₀ to the end-member majorite, the moduli are also approximately independent of composition, but at a lower value. An alternative model with a continuous decrease in moduli with increasing majorite content cannot be excluded, within the uncertainties of existing measurements. The contrast in moduli between aluminous pyrope garnet and Al-free majorite are small compared with the modulus changes accompanying the pyroxene – majorite phase transformation. Received August 16, 1995 /Revised, accepted January 12, 1996     

Byproduct Formation During the Reduction of TCE by Zero-Valence Iron and Palladized Iron

Trichloroethene (TCE) was reduced with zero-valence iron and palladized iron in zero-head-space extractors. Progress of the reaction in these batch studies was monitored with purge-and-trap gas chromatography and a flame ionization detector. When a 5 ppm initial concentration of TCF. reacts with zero-valence iron, approximately 140 ppb of vinyl chloride persists for as long as 73 days. The concentration of vinyl chloride (approximately If) ppb) remaining with palladized iron is approximately an order of magnitude less than when zero-valence iron is the reductant. These data suggest that volatile byproducts may be under-represented in oilier published data regarding reduction with zero-valence metals. These results also demonstrate that the reduction of TCE with palladized iron (0.05 percent palladium) is more than an order of magnitude faster than with zero-valence iron. Wilh a 5:1 solution-to-solid ratio the TCE half-life with zero-valence iron is 7.41 hours. but is only 0.59 hours with the palladized iron.     

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Fish Remains from Homestead Cave and Lake Levels of the Past 13,000 Years in the Bonneville Basin

A late Quaternary ichthyofauna from Homestead Cave, Utah, provides a new source of information on lake history in the Bonneville basin. The fish, represented by 11 freshwater species, were accumulated between 11,200 and 1000 ¹⁴C yr B.P. by scavenging owls. The ⁸⁷Sr/⁸⁶Sr ratio of Lake Bonneville varied with its elevation; ⁸⁷Sr/⁸⁶Sr values of fish from the lowest stratum of the cave suggest they grew in a lake near the terminal Pleistocene Gilbert shoreline. In the lowest deposits, a decrease in fish size and an increase in species tolerant of higher salinities or temperatures suggest multiple die-offs associated with declining lake levels. An initial, catastrophic, post-Provo die-off occurred at 11,300–11,200 ¹⁴C yr B.P. and was followed by at least one rebound or recolonization of fish populations, but fish were gone from Lake Bonneville sometime before 10,400 ¹⁴C yr B.P. This evidence is inconsistent with previous inferences of a near desiccation of Lake Bonneville between 13,000 and 12,000 ¹⁴C yr B.P. Peaks in Gila atraria frequencies in the upper strata suggest the Great Salt Lake had highstands at 3400 and 1000 ¹⁴C yr B.P.