Equilibrium interface segregation in the diopside-forsterite system I: Analytical techniques, thermodynamics, and segregation characteristics

After syntheses of partially molten diopside-forsterite polycrystalline aggregates doped with various solutes, we analyzed the equilibrium segregation of Ni, Mn, Sr, Al, Yb, Y, Nd, La, and Ti at interfaces between diopside/diopside, diopside/forsterite and, forsterite/forsterite grains based on STEM/EDX (scanning transmission electron microscopy/energy dispersive X-ray spectrometry) to examine the effects of ionic size, valence state, co-segregation, and interface type on interface chemistry. We derive relationships between two quantities describing interface segregation and X-ray intensities acquired both from areas that include an interface and from areas that do not. These segregation quantities are (i) interface excess density and (ii) interface enrichment factor, which rely on Gibbsian thermodynamics and the Langmuir-McLean segregation model, respectively. Interface excess densities, which vary from −0.5 to 10 atoms/nm², indicate that the level of interface excess density depends on solutes and sample assemblage. Interface enrichment factors, which range from almost 1 to 130, reveal that the ionic size of the solutes affects their segregation via production of misfit lattice strain due to the difference between the size of a solute ion and that of the ideal strain-free lattice site. The ionic sizes of Yb and Y are almost identical to the size of the strain-free site; however, their segregation is significant indicating that a difference in valence state between the host elements (i.e., Ca and Mg) and the solutes also drives segregation. In contrast to other solutes, segregation characteristics of Al differ from these simple segregation rules. Segregation quantities do not change with interface type, indicating that the number of sites available for segregants and the driving force for segregation are similar among type of interfaces. We compare the element partitioning between diopside-melt and diopside-interfaces within the same sample assemblages. These two partition coefficients coincide if we approximate the number of segregation sites at interfaces as equivalent to 2 mono-atomic layers. Examination of the energetics in crystal-melt partitioning reveals that the interface segregation energy is essentially equal to the solute solution energy in a crystal.     

The effects of soil type and chemical treatment on nickel speciation in refinery enriched soils: A multi-technique investigation

Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km² of land with Ni concentrations exceeding the Canadian Ministry of the Environment’s remedial action level of 200 mg kg⁻¹. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale ‘Kotodesh’, a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability.Stirred-flow dissolution experiments using pH 4 HNO₃ showed that Ni release from the limed Quarry muck and Welland loam soils was reduced (∼0.10%) relative to the unlimed soils (∼2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 μm in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils.The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne refinery. We provide the first evidence that Ni-Al LDH phases can form in anthropogenically enriched mineral field soils at circumneutral pH, and can lead to a reduction in Ni mobility. In the organic soils Ni is strongly complexed by soil organic matter; a property enhanced with liming. Interestingly, increased accumulation of Ni by A. murale grown in the limed muck and loam soils indicates that the plant may be capable of removing Ni from those fractions typically considered unavailable to most plants.     

Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca)

The mechanism and kinetics of superoxide-mediated reduction of a variety of organic iron(III) complexes has been investigated over the pH range 7-9. Our experimental results show that the rate of iron(II) formation is a function of pH, ligand type and ligand concentration with the measured rate varying between 0.44 ± 0.07 and 39.25 ± 1.77 pM s⁻¹ in the systems investigated. Additionally, our results show that the presence of competing cations such as Ca²⁺ have a significant impact on iron(II) formation if the organic ligand is strongly complexed by Ca²⁺. Formation of iron(II) occurs by either (or, in some instances, both) reaction of superoxide with inorganic iron(III) after its dissociation from the complex (dissociative reduction) or by direct reaction of superoxide with the complex (non-dissociative reduction). In the presence of weak ligands, dissociative reduction (DR) dominates; however non-dissociative reduction (NDR) becomes important in the presence of either strongly binding ligands or high concentrations of weakly binding ligands. The major factors contributing to the pH dependence of the iron(II) formation rate are the complexation kinetics of inorganic iron(III) (which controls the DR contribution) and the reduction kinetics of the iron(III) complex (which controls the NDR contribution). The relative NDR contribution increases with increasing superoxide and ligand concentration and decreasing pH for all ligands examined. Since iron(II) formation occurring via NDR results in a significantly larger increase in the proportion of iron in free aquated form than does DR, this non-dissociative pathway of superoxide-mediated iron(III) reduction is particularly effective in increasing the lability of iron in aquatic systems.     

Quaternary depositional patterns and sea-level fluctuations, northeastern North Carolina

A detailed record of late Quaternary sea-level oscillations is preserved within the upper 45 m of deposits along an eight km transect across Croatan Sound, a drowned tributary of the Roanoke/Albemarle drainage system, northeastern North Carolina. Drill-hole and seismic data reveal nine relatively complete sequences filling an antecedent valley comprised of discontinuous middle and early Pleistocene deposits. On interfluves, lithologically similar marine deposits of different sequences occur stacked in vertical succession and separated by ravinement surfaces. Within the paleo-drainage, marine deposits are separated by fluvial and/or estuarine sediments deposited during periods of lowered sea level. Foraminiferal and molluscan fossil assemblages indicate that marine facies were deposited in a shallow-marine embayment with open connection to shelf waters. Each sequence modifies or truncates portions of the preceding sequence or sequences. Sequence boundaries are the product of a combination of fluvial, estuarine, and marine erosional processes. Stratigraphic and age analyses constrain the ages of sequences to late Marine Isotope Stage (MIS) 6 and younger (∼ 140 ka to present), indicating multiple sea-level oscillations during this interval. Elevations of highstand deposits associated with late MIS 5 and MIS 3 imply that sea level was either similar to present during those times, or that the region may have been influenced by glacio-isostatic uplift and subsidence.     

Paleoproterozoic gold deposits in the Bald Hill and Coyote areas, Western Tanami, Western Australia

Significant gold deposits in the western Tanami region of Western Australia include deposits in the Bald Hill and Coyote areas. The ca. 1,864 Ma Bald Hill sequence of turbiditic and mafic volcanic rocks hosts the Kookaburra and Sandpiper deposits and a number of smaller prospects. The ca. 1,835 Ma turbiditic Killi Killi Formation hosts the Coyote deposit and several nearby prospects. The Kookaburra deposit forms as a saddle reef within a syncline, and the Sandpiper deposit is localized within graphitic metasedimentary rocks along a limb of an anticline. Gold in these deposits is hosted by anastomosing quartz–(–pyrite–arsenopyrite) veins within quartz–sericite schist with disseminated arsenopyrite, pyrite, and marcasite (after pyrrhotite). Based on relative timing relationships with structural elements, the auriferous veins are interpreted to have been emplaced before or during the ca. 1,835–1,825 Ma Tanami Orogeny (regional D₁). Gold deposition is thought to have been caused by pressure drops associated with saddle reef formation (Kookaburra) and chemical reactions with graphitic rocks (Sandpiper). The Coyote deposit, the largest in the western Tanami region, consists of a number of ore lenses localized along the limbs of the Coyote Anticline, which formed during the Tanami Orogeny. The largest lenses are associated with the Gonzalez Fault, which is located along the steeply dipping southern limb of this fold. Gold was introduced at ca. 1,790 Ma into dilatant zones that formed in local perturbations along this fault during later reactivation (regional D₅) towards the end of a period of granite emplacement. Gold is associated with quartz–chlorite–pyrite–(arsenopyrite–galena–sphalerite) veins with narrow (<?5 mm) chloritic selvages. A quartz–muscovite–biotite–K–feldspar–(tourmaline–actinolite–arsenopyrite) assemblage, which is interpreted to relate to granite emplacement, overprints the regional greenschist facies metamorphic assemblage. The mineralogical similarity between this overprinting assemblage and the vein assemblage suggests that the auriferous veins at the Coyote deposit are associated with the granite-related metamorphic–metasomatic assemblage. Gold deposition is thought to have been caused by pressure drops within dilatant zones.     

A method for generating uniform size-segregated pyrite particle fractions

Background  

Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest.     

Oceanography of Glacier Bay,Alaska: Implications for biological patterns in a glacial fjord estuary

Alaska, U.S.A, is one of the few remaining locations in the world that has fjords that contain temperate idewater glaciers. Studying such estuarine systems provides vital information on how deglaciation affects oceanographic onditions of fjords and surrounding coastal waters. The oceanographic system of Glacier Bay, Alaska, is of particular interest ue to the rapid deglaciation of the Bay and the resulting changes in the estuarine environment, the relatively high oncentrations of marine mammals, seabirds, fishes, and invertebrates, and the Bay’s status as a national park, where ommercial fisheries are being phased out. We describe the first comprehensive broad-scale analysis of physical and iological oceanographic conditions within Glacier Bay based on CTD measurements at 24 stations from 1993 to 2002. easonal patterns of near-surface salinity, temperature, stratification, turbidity, and euphotic depth suggest that freshwater nput was highest in summer, emphasizing the critical role of glacier and snowmelt to this system. Strong and persistent tratification of surface waters driven by freshwater input occurred from spring through fall. After accounting for seasonal nd spatial variation, several of the external physical factors (i.e., air temperature, precipitation, day length) explained a large mount of variation in the physical properties of the surface waters. Spatial patterns of phytoplankton biomass varied hroughout the year and were related to stratification levels, euphotic depth, and day length. We observed hydrographic atterns indicative of strong competing forces influencing water column stability within Glacier Bay: high levels of freshwater ischarge promoted stratification in the upper fjord, while strong tidal currents over the Bay’s shallow entrance sill enhanced ertical mixing. Where these two processes met in the central deep basins there were optimal conditions of intermediate tratification, higher light levels, and potential nutrient renewal. These conditions were associated with high and sustained hlorophylla levels observed from spring through fall in these zones of the Bay and provide a framework for understanding he abundance patterns of higher trophic levels within this estuarine system.     

Spatial and temporal variability of mesozooplankton and tintinnid ciliates in a seasonally hypersaline estuary

The zooplankton community of Mission Bay, San Diego, California, was monitored over two years, to study spatial and temporal patterns and the response of zooplankton species composition to environmental variation. Data were collected every two weeks from six stations and included hydrographic parameters, dissolved nutrient concentrations, and phytoplankton and zooplankton species composition. Hydrography varied seasonally, along a spatial gradient from the mouth to the back of the bay, and between the two years around the influence of rainfall. Spatially, Mission Bay could be divided into three regions during this study based on hydrography and zooplankton species composition. Zooplankton species composition followed a predictable seasonal progression, with different groups of species being characteristic to particular times of the year. Variability in zooplankton species composition was also evident between years, as certain species were more common in one or the other year of the study. Spatial patterns were more consistent than temporal ones, and related to distance from the mouth of the bay during much of the year and distance from freshwater inlets during the relatively short rainy season. Multivariate analysis revealed that variation in zooplankton species composition was best related to measured abiotic factors (temperature, salinity, rainfall, and tidal velocity).