Particulate iron and manganese in the Santa Barbara Basin,California

Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.     

Speciation and age revision of the Atacaman snail Bostryx variabilis Herm

Field evidence from the Atacama Desert of northern Chile indicates that the stratigraphic position of the land snail Bostryx variabilis Herm has been incorrectly assigned to a marine series of the lower Pleistocene. Isotopic dating proves that the snail is a recently extinct Holocene taxon requiring no special paleoenvironmental explanations for its presence. However, the snail appears to offer an example of stress-induced speciation in confirmation of the “punctuated equilibrium” theory of evolution. It was probably transported from a fog oasis mountain habitat to a lower, hyperarid hostile environment by a sudden mudflow.     

Kinetics and mechanisms of the reaction of zoisite to anorthite under hydrothermal conditions: reaction phenomenology away from the equilibrium region

The kinetics and mechanisms of the dehydration reactions of zoisite have been studied at 635°–792° C, 1–2 kbar. The equilibrium reaction does not occur and is replaced by metastable reactions involving the formation of gehlenite and a calcium tri-octahedral mica, instead of corundum: zoisite anorthite+grossular+gehlenite +calcium 3T mica+H₂O.The experimental data can be interpreted by zero-order equations dX _An/dt=k (X _An=fractional extent of reaction, t=time, k=zero-order rate constant). These relations hold for variations in P, T, A _initial(the initial surface area of zoisite) and also in the presence of seed crystals, which enhance the reaction rate. No induction period is evident and only at advanced stages of reaction are sharp decreases observed in the rate, which are attributed to physical affects (shrinking particles, armouring). SEM studies show that dissolution of zoisite is anisotropic, occurring preferentially parallel to the crystallographic b-axis, with the result that a characteristic sawtooth etch structure develops. Garnet grows as euhedral crystals located in cavities or on teeth of dissolving zoisite, whereas anorthite forms as clusters of coalescing grains which spread over and enclose the zoisite. In seeded runs, garnet growth initiates on both seeds and on zoisite surfaces whereas anorthite growth is more closely tied to the seeds, resulting in the development of clusters of smaller grains.The experimental evidence favours dissolution and nucleation-controlled growth as rate-determining processes. The preservation of zero-order kinetics in the face of shrinking particles is attributed to the anisotropic dissolution mechanism, which effectively preserves a constant reaction interface. The rate effects of nucleation appear to accord with the classic model in which growth of crystal layers is initiated by the formation of coherent nuclei.The temperature dependence of rate constants reflects both thermally activated Arrhenius-type behaviour and the rate-depressing influences of approach to equilibrium. Similarly pressure affects on reaction rate can be interpreted in terms of competition between rate enhancement due to pressure increase and rate-depression accompanying the approach to equilibrium. Although the equilibrium-approach effects accord with current treatments of reaction kinetics, a problem exists in deriving an exact relation coupling dissolution and nucleation rate control. Consequently an overall-reaction rate equation, such as that of Fisher and Lasaga (1981), is only partially successful in interpreting the temperature dependence of rates. The data suggest that the surface reaction equation of Wood and Walther (1983) only applies when nuclei are present.     

Lithic breccias in pyroclastic flow deposits on St. Kitts,West Indies

Lithic-rich breccias are described from within a sequence of young (2000–3000 yrs B.P.) scoria and ash flow deposits erupted from Mount Misery and an older pumice and ash flow deposit (ignimbrite) on St. Kitts. Cross sections constructed through pyroclastic flow fans in well-exposed sea cliffs 4–6 km from the vent show that the lithic breccias are lensoid deposits which seem to occur as channel-shaped accumulations (up to > 20 m thick and > 150 m wide) within flow units. The best-developed example infills a deeply incised channel cut into older flow units. The coarsest lithic breccias are clast supported and fines depleted and grade laterally and vertically through finer-grained, matrix-supported breccias into scoria and ash flow deposits. Coarse scoria-concentration zones mainly occur at the tops of scoria and ash flow units but also at the bases, and gas-segregation pipes are common. The lithic breccias are a type of body-concentration deposit as they pass laterally into normal scoria and ash flow deposits and, where best developed, clearly occur above a reversely graded basal shear zone or layer. Grain-size studies indicate the lithic breccias and parent flows are strongly fines depleted and were highly fluidized. We suggest this may be a feature of many Lesser Antillean pyroclastic flows because of increased turbulence-induced fluidization resulting from a high degree of surface roughness caused by the steep (up to 40 °) irregular slopes, densely vegetated sinuous gullies of the tropical volcanoes, and ingestion and ignition of large amounts of lush vegetation. Accumulation of batches of lithics concentrated in the highly fluidized flows began at the break in slope where flows moved from gullies across hydraulic jumps onto the outer coastal flanks. The accumulations of breccias continued to move and be channelled down the central parts of the flows. Initially, on crossing onto the lower slopes, some of these flows seem to have had very powerfully erosive, nondepositional heads, and in the extreme example a deep channel as long as 1–2 km may have cut through underlying flow units at least as far as the present coastline. Much of the overriding remainder of the flow then drained away laterally. Thin, fine-grained ash flow deposits may form a marginal overbank facies to the pyroclastic flow fans.     

Response of secondary systems in structures subjected to transient excitation

An analytical method, based on matrix perturbation theory, is developed whereby a simple estimate can be obtained of the maximum dynamic response of lightly damped, light equipment (modelled as a n(²)-degree-of-freedom system) attached to a structure (modelled as a n(¹)-degree-of-freedom system) subjected to ground motion or impact. A natural frequency of the equipment is considered close or equal to a natural frequency of the structure. It is assumed that the information available to the designer is a time history of the ground motion or impact, or an associated design spectrum; the fixed base modal properties of the structure; and the fixed base modal properties of the equipment. The method employed avoids the direct conventional analysis of a n(²) + n(¹)-degree-of-freedom system either by modal or by matrix time-marching methods; as well as errors in estimates of peak response due to the possible unreliability of numerical schemes because of the lightness of the equipment, or due to uncertainty as to the appropriate procedure for summing the contributions of the two closely spaced modes which occur in the system. The proposed procedure is demonstrated for an example equipment-structure system. Computed results based on the method are in close agreement with results obtained through a Newmark time-integration scheme.     

The geochemical behavior of refractory noble metals and lithophile trace elements in refractory inclusions in carbonaceous chondrites

Recent models of Ca, Al-rich inclusion (CAI) petrogenesis suggest that refractory inclusions may be residues of interstellar dust aggregates that were incompletely evaporated and partially melted in the solar nebula. These models, and the recent availability of new thermodynamic data, have led us to re-examine the traditional interpretation that lithophile refractory trace elements (LRTE) condensed as oxides in solid solution in refractory major condensates, while refractory noble metals (RNM) condensed as micron-sized nuggets of Pt-metal alloys. Calculations of LRTE-RNM alloy stability fields under nebular oxygen fugacities and partitioning experiments lead us to conclude that: (1) Ti, Zr, Nb, Hf, U, and Ta form stable alloys with RNM under nebular conditions; (2) the observation that metallic Zr, Nb, and Ta occur in some Pt-metal nuggets and grains is explained by the stability of these LRTE-RNM alloys under normal nebular oxygen fugacities; (3) metallic Ti, Hf, and U may also occur in some nuggets; (4) the lanthanides, the other actinides (Th, Pu), and Y do not form stable alloys, and thus probably do not occur alloyed with RNM; and (5) the partitioning of U (but not Th, Pu, or the REE) into RNM is a novel actinide and REE/actinide fractionation mechanism that is based on metal/silicate fractionation (rather than on the relative volatility of their oxides).We propose that micron-sized Pt-metal nuggets formed from smaller grains of RNM alloys and compounds during the evaporation and melting of primitive dust aggregates. This process would have been enhanced by: (1) the possibility that the RNM were present as compounds (especially with As and S) as well as metallic alloys in interstellar dust and in some primitive meteoritical material, since they often exhibit non-siderophile behavior; and (2) the fluxing of volatiles through CAI's during distillation. Microscopic nuggets are common in melilite chondrules, indicating that residence in a slowly-cooled silicate melt may have favored their formation. Cation diffusivity and variations in localf_O2 can explain why metallic LRTE-bearing nuggets are not common in CAI's (despite the relative stability of LRTE-RNM alloys). We propose that the lithophile component of Fremdlinge is enriched in super-refractory elements, and that Group II CAI's formed from Fremdlinge-poor dust. We interpret the Group II REE fractionation as a pre-solar event, and predict that Nd/Sm dating will yield an age greater than the canonical age of the solar system. If metal/silicate fractionation in a cold solar nebula can explain Group II REE patterns, the possibility that Group II CAI's are also distillation residues cannot be excluded.     

Matrix material in type 3 chondrites—occurrence,heterogeneity and relationship with chondrules

Matrix material in type 3 chondrites forms rims on chondrules, metal-sulfide aggregates, Ca,Al-rich inclusions and chondritic clasts; it also forms lumps up to a millimeter in size, which may contain coarser silicates. Chondrules of all types were found with internal matrix lumps that appear to have entered the chondrules before the latter had crystallized. Mean concentrations of Mg, Na, Al and Ca in matrix occurrences show up to fivefold variations in a single chondrite. Variations between mean matrix compositions of individual type 3 ordinary chondrites are almost as large and partly reflect systematic differences between H, L and LL matrices. Such variations are probably a result of nebular separation of feldspathic material and ferromagnesian silicates.Compositions of chondrules and their matrix rims are normally unrelated, although rim compositions are correlated with those of matrix lumps inside chondrules. A single chondrule was found with a composition nearly identical to that of its internal matrix lump, suggesting that some chondrules may have formed from matrix material. Matrix lumps are as heterogeneous as chondrules, but mean chondrule and matrix compositions differ, even allowing for possible loss of metallic Fe,Ni during chondrule formation. Since bulk compositions of matrix lumps and rims have probably not changed significantly since their formation except for Fe-Mg exchange, our matrix samples cannot represent typical chondrule precursor materials.