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.     

Fluid generation and evolution during exhumation of deeply subducted UHP continental crust: Petrogenesis of composite granite–quartz veins in the Sulu belt,China

Composite granite–quartz veins occur in retrogressed ultrahigh pressure (UHP) eclogite enclosed in gneiss at General's Hill in the central Sulu belt, eastern China. The granite in the veins has a high‐pressure (HP) mineral assemblage of dominantly quartz+phengite+allanite/epidote+garnet that yields pressures of 2.5–2.1 GPa (Si‐in‐phengite barometry) and temperatures of 850–780°C (Ti‐in‐zircon thermometry) at 2.5 GPa (~20°C lower at 2.1 GPa). Zircon overgrowths on inherited cores and new grains of zircon from both components of the composite veins crystallized at c. 221 Ma. This age overlaps the timing of HP retrograde recrystallization dated at 225–215 Ma from multiple localities in the Sulu belt, consistent with the HP conditions retrieved from the granite. The ε_Hf(t) values of new zircon from both components of the composite veins and the Sr–Nd isotope compositions of the granite consistently lie between values for gneiss and eclogite, whereas δ¹⁸O values of new zircon are similar in the veins and the crustal rocks. These data are consistent with zircon growth from a blended fluid generated internally within the gneiss and the eclogite, without any ingress of fluid from an external source. However, at the peak metamorphic pressure, which could have reached 7 GPa, the rocks were likely fluid absent. During initial exhumation under UHP conditions, exsolution of H₂O from nominally anhydrous minerals generated a grain boundary supercritical fluid in both gneiss and eclogite. As exhumation progressed, the volume of fluid increased allowing it to migrate by diffusing porous flow from grain boundaries into channels and drain from the dominant gneiss through the subordinate eclogite. This produced a blended fluid intermediate in its isotope composition between the two end‐members, as recorded by the composite veins. During exhumation from UHP (coesite) eclogite to HP (quartz) eclogite facies conditions, the supercritical fluid evolved by dissolution of the silicate mineral matrix, becoming increasingly solute‐rich, more ‘granitic’ and more viscous until it became trapped. As crystallization began by diffusive loss of H₂O to the host eclogite concomitant with ongoing exhumation of the crust, the trapped supercritical fluid intersected the solvus for the granite–H₂O system, allowing phase separation and formation of the composite granite–quartz veins. Subsequently, during the transition from HP eclogite to amphibolite facies conditions, minor phengite breakdown melting is recorded in both the granite and the gneiss by K‐feldspar+plagioclase+biotite aggregates located around phengite and by K‐feldspar veinlets along grain boundaries. Phase equilibria modelling of the granite indicates that this late‐stage melting records P–T conditions towards the end of the exhumation, with the subsolidus assemblage yielding 0.7–1.1 GPa at <670°C. Thus, the composite granite–quartz veins represent a rare example of a natural system recording how the fluid phase evolved during exhumation of continental crust. The successive availability of different fluid phases attending retrograde metamorphism from UHP eclogite to amphibolite facies conditions will affect the transport of trace elements through the continental crust and the role of these fluids as metasomatic agents interacting with the mantle wedge in the subduction channel.     

SPATIAL PATTERNS OF SUPPORT FOR A NUCLEAR WEAPONS FREEZE*

Support for a Freeze on nuclear weapons is greatest in the East with pockets of support in the Middle West and Pacific Coast States. Factors influencing the spatial pattern are Walker's innovativeness rankings, the number of peace/Freeze activist groups and the pattern of defense employment.     

Displacement-length scaling relations for faults on the terrestrial planets

Displacement-length (D/L)scaling relations for normal and thrust faults from Mars, and thrust faults from Mercury, for which sufficiently accurate measurements are available, are consistently smaller than terrestrial D/L ratios by a factor of about 5, regardless of fault type (i.e. normal or thrust). We demonstrate that D/L ratios for faults scale, to first order, with planetary gravity. In particular, confining pressure modulates: (1) the magnitude of shear driving stress on the fault; (2) the shear yield strength of near-tip rock; and (3) the Young's (or shear) modulus of crustal rock. In general, all three factors decrease with gravity for the same rock type and pore-pressure state (e.g. wet conditions). Faults on planets with lower surface gravities, such as Mars and Mercury, demonstrate systematically smaller D/L ratios than faults on larger planets, such as Earth. Smaller D/L ratios of faults on Venus and the Moon are predicted by this approach, and we infer still smaller values of D/L ratio for faults on icy satellites in the outer solar system. Collection of additional displacement-length and down-dip height data from terrestrial normal, strike-slip, and thrust faults, located within fold-and-thrust belts, plate margins, and continental interiors, is required to evaluate the influence of fault shape and progressive deformation on the scaling relations for faults from Earth and elsewhere.     

The origin and diagenesis of cherts from Cyprus

The Troodos Massif of Cyprus is overlain by a variety of cherts in pelagic chalks, volcanogenic sediments, radiolarites and radiolarian mudstones, all of Campanian to Upper Eocene age. There are two chert types, granular chert and vitreous chert. X-ray diffraction (XRD) reveals the silica polymorphs, disordered cristobalite and quartz. Silicification of the chalks varies from incipient, to bedded, granular cherts, all with disordered cristobalite as the main silica phase. Quartzitic cherts are restricted to the base of Upper Palaeocene and Lower Eocene calciturbidite beds. Disordered cristobalite predominates in the radiolarian mudstones at the foot of the sequence. The form of disordered cristobalite in cavities ranges from microspherules of radiating bladed crystals, the ‘lepispheres’ of the Deep Sea Drilling Project (DSDP) to bladed overgrowths, and fibrous silica. In contrast, within the fine grained matrix, the disordered cristobalite takes the form of partly coalescent crude microgranules and microspherules. Most of the chalcedonic quartz in Cyprus is derived by recrystallization of previously inorganically precipitated disordered cristobalite rather than by direct precipitation. According to the concept of impurity-controlled maturation the composition of host sediment controls the incorporation of exchangeable cations and other impurities into inorganically precipitated disordered cristobalite. With time (up to 100 million years) internal solid state reorganization of the disordered cristobalite is accompanied by gradual expulsion of impurities, until the cristobalite dissolves followed by quartz precipitation. Complete conversion to quartz takes place first in porous calcareous sediments free of impurities, as in the Cyprus calciturbidites; in fine grained clay-rich sediments, like Cyprus radiolarian mudstones, disordered cristobalite persists much longer. Impurity-controlled maturation also helps explain the diagenesis of Cyprus chert nodules.     

Wave forces on, and water-surface fluctuations around a vertical cylinder encircled by a perforated square caisson

The wave forces and moments on and the water surface fluctuations around a vertical circular cylinder encircled by a perforated square caisson were experimentally investigated. The porosity of the outer square caisson was varied from 4.24 to 14.58%. The in-line wave forces on the inner vertical cylinder are influenced by changing the porosity of the outer caisson, whereas the variations in the water surface fluctuations are less influenced in this porosity range. The in-line moment on the vertical cylinder is relatively less sensitive when the porosity is increased from 4.24 to 8.75%, but varies substantially when it is increased from 8.75 to 14.58%. The force and moment ratio (i.e. the ratio of the force or moment on the vertical cylinder, when it is encircled by the perforated caisson to the force or moment on the cylinder without any protection around it) reduces with increased wave height, H, and wave length, L, whereas the wave height ratio (ratio of the wave height at a point in the vicinity of the structure to the incident wave height) is less sensitive for the varying H and L. A new non-dimensional parameter, p^1.5 (D/L)/(H/d), is introduced to predict the in-line force and moment on the inner vertical cylinder, where d is local water depth, D is the diameter of the inner cylinder and p is the porosity of the outer caisson in percentage. Simple predictive equations for forces, moments and water surface fluctuations are provided.