CHEMO-PLASTICITY OF CLAYS SUBJECTED TO STRESS AND FLOW OF A SINGLE CONTAMINANT

Isothermal chemo-elasto-plasticity of clays is discussed, to describe strains induced in clay by permeation of it with a low dielectric constant organic contaminant, in the presence of stress. The strain is crucial in controlling permeability changes in chemically affected clay barriers of landfills and impoundments. The theory encompasses chemical softening or yield surface reduction, coefficient of chemical reversible expansion or contraction due to mass concentration increase, as well as chemical sensitivity of bulk plastic modulus. The experiments on chemistry and stress dependent permeability of Sarnia clay performed by Fernandez and Quigley (1985, 1991) are interpreted using this model. The numerical representations of the chemo-plastic softening function and the chemo-elastic strain function, as well as plastic bulk modulus sensitivity to concentration are evaluated for dioxane and ethanol. Specific requirements for the tests for chemo-plastic behavior of clays are discussed. © 1997 by John Wiley & Sons, Ltd.     

High-Mg# andesitic lavas of the Shisheisky Complex,Northern Kamchatka: implications for primitive calc-alkaline magmatism

Primitive arc magmatism and mantle wedge processes are investigated through a petrologic and geochemical study of high-Mg# (Mg/Mg + Fe > 0.65) basalts, basaltic andesites and andesites from the Kurile-Kamchatka subduction system. Primitive andesitic samples are from the Shisheisky Complex, a field of Quaternary-age, monogenetic cones located in the Aleutian–Kamchatka junction, north of Shiveluch Volcano, the northernmost active composite volcano in Kamchatka. The Shisheisky lavas have Mg# of 0.66–0.73 at intermediate SiO₂ (54–58 wt%) with low CaO (<8.8%), CaO/Al₂O₃ (<0.54), and relatively high Na₂O (>3.0 wt%) and K₂O (>1.0 wt%). Olivine phenocryst core compositions of Fo90 appear to be in equilibrium with whole-rock ‘melts’, consistent with the sparsely phyric nature of the lavas. Compared to the Shisheisky andesites, primitive basalts from the region (Kuriles, Tolbachik, Kharchinsky) have higher CaO (>9.9 wt%) and CaO/Al₂O₃ (>0.60), and lower whole-rock Na₂O (<2.7 wt%) and K₂O (<1.1 wt%) at similar Mg# (0.66–0.70). Olivine phenocrysts in basalts have in general, higher CaO and Mn/Fe and lower Ni and Ni/Mg at Fo88 compared to the andesites. The absence of plagioclase phenocrysts from the primitive andesitic lavas contrasts the plagioclase-phyric basalts, indicating relatively high pre-eruptive water contents for the primitive andesitic magmas compared to basalts. Estimated temperature and water contents for primitive basaltic andesites and andesites are 984–1,143°C and 4–7 wt% H₂O. For primitive basalts they are 1,149–1,227°C and 2 wt% H₂O. Petrographic and mineral compositions suggest that the primitive andesitic lavas were liquids in equilibrium with mantle peridotite and were not produced by mixing between basalts and felsic crustal melts, contamination by xenocrystic olivine, or crystal fractionation of basalt. Key geochemical features of the Shisheisky primitive lavas (high Ni/MgO, Na₂O, Ni/Yb and Mg# at intermediate SiO₂) combined with the location of the volcanic field above the edge of the subducting Pacific Plate support a genetic model that involves melting of eclogite or pyroxenite at or near the surface of the subducting plate, followed by interaction of that melt with hotter peridotite in the over-lying mantle wedge. The strongly calc-alkaline igneous series at Shiveluch Volcano is interpreted to result from the emplacement and evolution of primitive andesitic magmas similar to those that are present in nearby monogenetic cones of the Shisheisky Complex.     

Solubility of water-hydrogen fluid in haplogranite,albite, and sodium disilicate melts

Solubility curves of water-hydrogen fluid were studied using a high-pressure gas apparatus at a pressure of 200 MPa under variable fluid composition in haplogranite (Ab ₃₉ Or ₃₂ Qtz ₂₉, 950°C), Na-disilicate (Na₂Si₂O₅, 950°C), and albite melts (1200°C). The mole fraction of hydrogen in experiments was controlled directly by Ar-H₂ mixtures using a specially designed cell with a Shaw membrane. $ X_{H_2 }^{Ar - H_2 } $ X_{H_2 }^{Ar - H_2 } ranged from 0 to 1. In some experiments with haplogranite and Na-disilicate melts under oxidizing conditions, in order to increase the accuracy of experimental parameters, the fugacities of oxygen and hydrogen were controlled using the double-capsule technique and the solid-phase buffer mixtures Ni-NiO (NNO) and Co-CoO (CCO). The addition of H₂ to the H₂O-saturated systems ($ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } ≥ 0.012) results in the appearance of a distinct maximum on the solubility curves at $ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } = 0.05–0.07 (H₂ mole fractions were calculated for real H₂O-H₂ mixtures of real gases), and the maximum content of H₂O-H₂ fluid increases relative to the H₂O-saturated melts by 1.51 wt % for haplogranite melt at $ X_{H_2 } $ X_{H_2 } = 0.063, 2.68 wt % for albite melt at $ X_{H_2 } $ X_{H_2 } = 0.066, and 3.54 wt % for Na-disilicate melt at $ X_{H_2 } $ X_{H_2 } = 0.067. A further increase in H₂ content in the gas mixture decreases the solubility of H₂O-H₂ fluid in the melts, and under pure H₂ pressure, the contents of fluid components are 0.08 wt % in haplogranite melt and 0.06 wt % in albite melt. The ¹H NMR study of aluminosilicate and Na-silicate glasses obtained under the pressure of H₂O and H₂O-H₂ fluids suggests different mechanisms of the dissolution of H₂O and H₂O-H₂ fluids in magmatic melts. In addition to the spectra of dissolved water fluid, the spectra of quenched glasses synthesized under H₂O-H₂ fluid pressure exhibited a narrow line of molecular hydrogen with a width at half height of 1.8–2.0 kHz at $ X_{H_2 } $ X_{H_2 } ≥ 0.653 for albite and $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for Na-disilicate and two lines at $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for the haplogranite composition.     

Mechanical aspects of sedimentary basin formation: development of integrated models for lithospheric and surface processes

Different assumptions for the thermo-mechanical properties of the lithosphere strongly affect predictions inferred from quantitative sedimentary basin modeling. Examples from various basins, selected as natural laboratories, illustrate the importance of incorporating a finite strength of the extending lithosphere in forward stratigraphic modeling of large-scale basin stratigraphy. Current models can effectively couple erosion at uplifted rift shoulders of extensional basins with the basin fill architecture of the subsiding basin compartments. Modeling of the synrift strata integrates spatial scales characteristic for subbasins, such as the Oseberg field in the North Sea, with large-scale lithospheric properties characterizing the bulk strength of extending lithosphere. Modeling of compressional basins in foreland fold-and-thrust-belt settings can effectively link lithospheric flexure with surface processes. Scales pertinent to short-term spatial and temporal variations in basin fill and basin deformation can now be addressed, allowing the quantitative investigation of consequences of different modes of thrusting for basin fill geometry and facies characteristics.     

A PRELIMINARY REPORT OF ARCHAEOLOGICAL INVESTIGATIONS ON THE SINO-TIBETAN BORDER OF SZECHWAN§

INTRODUCTION During the year 1930-31, while holding a schularship from the Harvard-Yenching Institute, I received permission from the Institute to engage in ethnological and anthropological research on behalf of the University Museum     

Pilot study experiments sourcing quartzite,Gunnison Basin,Colorado

This paper reports the results of pilot‐study efforts to develop methods to profile quartzite, a rock type to which geochemical and other sourcing techniques have only rarely been applied. The long‐term goal of the research is to fingerprint sources of quartzite in the Gunnison Basin, southwest Colorado, used by Paleoindian people ca. 11,500–8,000 years ago to make stone tools. Success would facilitate reconstruction of Paleoindian mobility in the Southern Rocky Mountains and potentially anywhere prehistoric people used quartzite. The goals of this paper are more modest: to demonstrate that a small‐scale exploration of sourcing techniques suggests reason for optimism that quartzites may be amenable to source discrimination. For the same twenty Gunnison Basin quartzite samples, this study evaluated petrography, ultraviolet fluorescence (UVF), wavelength dispersive X‐ray fluorescence (WD‐XRF), instrumental neutron activation analysis (INAA), and inductively coupled plasma mass spectrometry—both acid‐digestion (AD‐ICP‐MS) and laser ablation (LA‐ICP‐MS)—as means to differentiate among the specimens and the sources they represent. Although more testing is needed to verify and refine our results, the study suggests there is potential for petrography, INAA, and both versions of ICP‐MS to discriminate among quartzites from different source localities in the Gunnison Basin. The greatest potential for discriminating among different sources of quartzite in the Gunnison Basin may lie in a methodology combining petrographic analysis and LA‐ICPMS. Future testing is required to evaluate this two‐fold approach. © 2008 Wiley Periodicals, Inc.     

Influence of wave and sediment dynamics on cordgrass (<Emphasis Type="Italic">Spartina anglica</Emphasis>) growth and sediment accumulation on an exposed intertidal flat

Isolated patches ofSpartina anglica (cordgrass) at two sites on a wave-exposed mid-intertidal flat of the 340 km² Manukau Harbor (Auckland, New Zealand) have developed very differently since being planted in the mid-1970s. Although the two sites are only 0.5 km apart and at the same intertidal elevation,Spartina patches at the easternmost site (site 1) have as much as an order of magnitude higher biomass and accumulated sediment volume thanSpartina patches at site 2. A field experiment was conducted to characterize waves and associated sediment dynamics at each site, which might explain whySpartina patches at the two sites have developed so differently over the past 25 yr or so. Suspended sediments were measured and wave characteristics were inferred from subsurface pressure data measured for 5 wk at bothSpartina sites and at an intermediate location. Bed-orbital speeds and frictional wave-energy dissipation were consistently lower at the easternmost site with the largerSpartina patches. The west-to-east reduction in wave energy is due to the spatial arrangement of theSpartina sites relative to the predominant wind fetches. The wave-energy gradient is maintained by tidal-cycle variations in fetch and bed friction and results in a west-to-east reduction in sand suspension. Silt, which is largely resuspended under southwest winds, is redeposited in the low wave-energy conditions in and around the larger site 1Spartina patches. Shell accumulation bySpartina patches at site 1 occurs infrequently, during southwest winds >10 m s⁻¹ and water depths >0.7 m, when waves are least attenuated by bed friction. Large between-site differences in the growth of and sediment accumulation by theSpartina patch are consistent with the observed wave-energy gradient. The resulting spatial patterns of silt, sand, and shell resuspension and deposition directly influence the rate of sediment accumulation bySpartina patches and the composition of accumulated sediment on this wave-exposed intertidal flat.     

Fish assemblage stability over fifty years in the Lake Pontchartrain estuary; Comparisons among habitats using canonical correspondence analysis

We assessed fish assemblage stability over the last half century in Lake Pontchartrain, an environmentally degraded oligohaline estuary in southeastern Louisiana. Because assemblage instability over time has been consistently associated with severe habitat degradation, we attempted to determine whether fish assemblages in demersal, nearshore, and pelagic habitats exhibited change that was unrelated to natural fluctuations in environmental variables (e.g., assemblage changes between wet and dry periods). Collection data from three gear types (trawl, beach seine, and gill nets) and monthly environmental data (salinity, temperature, and Secchi depth) were compared for four collecting periods: 1954 (dry period), 1978 (wet period), 1996–1998 (wet period), and 1998–2000 (dry period). Canonical correspondence analysis (CCA) revealed that although the three environmental variables were significantly associated with the distribution and abundance patterns of fish assemblages in all habitats (with the exception of Secchi depth for pelagic samples), most fish assemblage change occurred among sampling periods (i.e., along a temporal gradient unrelated to changing environmental variables). Assemblage instability was the most pronounced for fishes collected by trawls from demersal habitats. A marked lack of cyclicity in the trawl data CCA diagram indicated a shift away from a baseline demersal assemblage of 50 yr ago. Centroid positions for the five most collected species indicated that three benthic fishes, Atlantic croaker (Micropogonias undulatus), spot (Leiostomus xanthurus), and hardhead catfish (Arius felis), were more dominant in past demersal assemblages (1954 and 1978). A different situation was shown for planktivorous species collected by trawls with bay anchovy (Anchoa mitchilli) becoming more dominant in recent assemblage and Gulf menhaden (Brevoortia patromus) remaining equally represented in assemblages over time. Changes in fish assemblages from nearshore (beach seine) and pelagic (gill net) habitats were more closely related to environmental fluctuations, though the CCA for beach seine data also indicated a decrease in the dominance ofM. undulatus and an increase in the proportion ofA. mitchilli over time. The reduced assemblage role of benthic fishes and the marked assemblage change indicated by trawl data suggest that over the last half century demersal habitats in Lake Pontchartrain have been impacted more by multiple anthropogenic stressors than nearshore or pelagic habitats.     

The soft-bottom macrobenthos of North Carolina estuaries

The structure of macro infaunal (>0.5 mm sieve size) assemblages was examined in samples of unconsolidated substrates collected during the summers of 1994–1997 at 208 stations throughout North Carolina estuaries. Numerical classification (cluster analysis) of stations resulted in 14 distinct site groups that reflected discernible habitatrelated patterns in species distributions. Multiple discriminant analysis, performed on synoptic abiotic variables (depth, salinity, dissolved oxygen, pH, percent silt-clay), showed that the separation of site groups was related primarily to salinity. Percent silt-clay had a secondary influence on the separation of sites within similar salinity zones. Species diversity among site groups generally decreased with decreasing salinity and increasing mud content of sediment. Nodal analysis showed a wide range in constancy and fidelity of species assemblages within site groups. Some assemblages dominated by euryhaline species had no particular affinity with any one site group. The strongest affinities, as evidenced by high values of both constancy and fidelity, were displayed by an assemblage of oligochaetes, insect larvae, gammaridean amphipods, and the clamCorbicula fluminea in tidal freshwater muds; and an assemblage of haustoriid amphipods, the bivalveDonax variabilis, the polychaeteParaonis fulgens, and unidentified echinoids at high-salinity sites in outer Pamlico Sound near ocean inlets. A series of stations with impaired benthic assemblages in polluted habitats emerged from the cluster analysis and was distinguishable from other site groups that reflected a greater influence of natural controlling factors (such as salinity and sediment type) on species distributions. These results suggest that the interaction of both anthropogenic and natural environmental controlling factors is important in defining the structure of these infaunal assemblages.     

Pb diffusion in monazite: a combined RBS/SIMS study

We report measurements of Pb diffusion in both synthetic (CePO₄) and natural monazites run under dry, 1-atm conditions. Powdered mixtures of prereacted CePO₄ and PbZrO₃ were used as the source of Pb diffusant for “in-diffusion” experiments conducted in sealed Pt capsules for durations ranging from a few hours to several weeks. Following the diffusion anneals, Pb concentration profiles were measured with Rutherford Backscattering Spectroscopy (RBS) and supplemented by measurements with secondary ion mass spectrometry (SIMS). In order to evaluate potential compositional effects upon Pb diffusivity and simulate diffusional Pb loss that might occur in natural systems, we also conducted “out-diffusion” experiments on Pb-bearing natural monazites. In these experiments, monazite grains were surrounded by a synthetic zircon powder to act as a “sink.” Monazites from these experiments were analyzed with SIMS. Over the temperature range 1100 to 1350°C, the Arrhenius relation determined for in-diffusion experiments on synthetic monazite is given by: