Use of solid phase characterisation and chemical modelling for assessing the behaviour of arsenic in contaminated soils

A soil, containing waste material from an industrially contaminated site, was found to be heavily contaminated with several heavy metals and As. A risk assessment for As leaching from this material has been carried out in several stages, collation and examination of historical records, solid-phase characterization and chemical modelling. The historical record indicates that the most probable source of As was arsenopyrite. However, the solid phase characterization of the soil, using X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive microanalysis (EDAX), did not yield any direct evidence for pyritic phases, although there was clear evidence of known pyrite-weathering products, such as jarosite. The relative stability of pyrite and arsenopyrite have been modelled for the range of acidity and redox potentials likely to be encountered on the site. For adsorption modelling, a surface complexation model was used to predict arsenate desorption as a function of pH. It was assumed that the principal reactive adsorbent for As was hydrous ferric oxide (HFO) and this assumption was supported by the results of direct and indirect measurements and by the mineral stability calculations. This approach was successful at predicting the increased mobility of As at increasingly alkaline conditions. The modelling predictions were supported by results from batch equilibration experiments. Thus, it was possible to link direct observations of mineralogy, mineral stability calculations and adsorption models in order to predict the mobility of As. The success of this approach was dependent on identifying the reactive phase in this particular soil and having the appropriate data required for the adsorption modelling.     

Monazite as a monitor of melting,garnet growth and feldspar recrystallization in continental lower crust

Monazite is a common accessory phase in felsic granulite ribbon mylonites exposed in the Upper Deck domain of the Athabasca granulite terrane, western Canadian Shield. Field relationships, bulk rock geochemistry and phase equilibria modelling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ system are consistent with the garnet‐rich rocks representing the residual products of ultrahigh temperature melting of biotite‐bearing paragneisses driven by intraplating of mafic magma in continental lower crust. The c. 2.64–2.61 Ga Y‐rich resorbed monazite cores included in garnet are interpreted as relicts of detrital grains deposited on the Earth's surface after c. 2.61 Ga. Yttrium‐poor monazite domains in garnet are depleted in Sm and Gd and linked to fluid‐absent melting of biotite + plagioclase + quartz ± sillimanite during a prograde loading path from ≤0.8 to ≥1.4 GPa. The c. 2.61–2.55 Ga Y‐depleted, Th‐rich monazite domains crystallized in the presence of garnet + ternary feldspar ± orthopyroxene + peraluminous melt. The c. 2.58–2.52 Ga monazite rims depleted in Th + Ca and enriched in Eu are linked to localized melt extraction synchronous with growth of high‐pressure (HP) grossular‐rich garnet at the expense of plagioclase during crustal thickening, culminating at >950 °C. Re‐heating and dextral transpressive lower crustal reactivation at c. 1.9 Ga resulted in syn‐kinematic growth of (La + Ce)‐enriched monazite and a second generation of garnet, concurrent with recrystallization of feldspar and orthopyroxene at 1.0–1.2 GPa and 600–700 °C. Monazite grains in this study are marked by positive Eu‐anomalies relative to chondrite. A direct link is implied between Y, Sm, Eu and Gd in monazite and two major phases in continental lower crust: garnet and plagioclase. Positive Eu‐anomalies in lower crustal monazite associated with modally abundant garnet appear to be directly related to Eu‐enrichment and depletions of Y, Sm and Gd that are consequences of garnet growth and plagioclase breakdown during HP melting of peraluminous bulk compositions.     

Dynamic recrystallization and chemical evolution of clinoamphibole from Senja,Norway

Clinoamphibole from a mylonitic amphibolite exhibits microstructures characteristic of dynamic recrystallization, including porphyroclasts in a finer grained matrix of needle-shaped amphibole. The matrix amphibole defines an LS fabric and porphyroclasts have core and mantle structures with a core containing undulose to patchy extinction and (100) deformation twinning surrounded by a mantle of recrystallized grains. In addition intragranular grains also occur within the cores. TEM analyses of the porphyroclasts reveal that they contain a wide variety of lattice defects including high densities (5 × 10⁸cm^–2) of free dislocations and dislocation arrays, dissociated dislocations, stacking faults, and (100) micro-twins. TEM also shows that matrix grains and intragranular grains have relatively low defect densities, and that the intragranular new grains occur at localities in the porphyroclasts characterized by high densities of dislocations. These observations along with the chemical and orientation relationships between the recrystallized grains and porphyroclasts indicate that the new grains may have formed by heterogeneous nucleation and that further growth probably occurred by both strain assisted and chemically induced grain boundary migration or liquid film migration. This recrystallization event is interpreted to be synkinematic based on the fact that no recrystallization textures are present in the matrix grains and that the matrix grains define an LS fabric. However, the low defect densities in the matrix grains and the lack of intracrystalline strain in other phases indicate that post-kinematic recovery processes were active.     

Nanoscale resetting of the Th/Pb system in an isotopically-closed monazite grain: A combined atom probe and transmission electron microscopy study

Understanding the mechanisms of parent-daughter isotopic mobility at the nanoscale is key to rigorous interpretation of Ue The Pb data and associated dating. Until now, all nanoscale geochronological studies on geological samples have relied on either Transmission Electron Microscope(TEM) or Atom Probe Microscopy(APM) characterizations alone, thus suffering from the respective weaknesses of each technique. Here we focus on monazite crystals from a ~1 Ga, ultrahigh temperature granulite from Rogaland(Norway). This sample has recorded concordant UeP b dates(measured by LA-ICP-MS) that range over 100 My, with the three domains yielding distinct isotopic Ue Pb ages of 1034 ± 6 Ma(D1; Srich core), 1005 ± 7 Ma(D2), and 935 ± 7 Ma(D3), respectively. Combined APM and TEM characterization of these monazite crystals reveal phase separation that led to the isolation of two different radiogenic Pb(Pb*) reservoirs at the nanoscale. The S-rich core of these monazite crystals contains Cae Srich clusters, 5 -10 nm in size, homogenously distributed within the monazite matrix with a mean interparticle distance of 40 -60 nm. The clusters acted as a sink for radiogenic Pb(Pb*) produced in the monazite matrix, which was reset at the nanoscale via Pb diffusion while the grain remained closed at the micro-scale. Compared to the concordant ages given by conventional micro-scale dating of the grain,the apparent nano-scale age of the monazite matrix in between clusters is about 100 Myr younger, which compares remarkably well to the duration of the metamorphic event. This study highlights the capabilities of combined APM-TEM nano-structural and nano-isotopic characterizations in dating and timing of geological events, allowing the detection of processes untraceable with conventional dating methods.     

SPE-HPLC法测定大豆中二甲戊乐灵残留量

采用SPE-HPLC法测定了大豆中二甲戊乐灵的残留量,方法线性范围为1.0～10.0 mg/L,检出限为0.037 5mg/kg,精密度在3.78%～8.36%之间,回收率在86.0%～97.5%之间。满足大豆中二甲戊乐灵农药残留的检测要求。     

Prediction of solid/liquid distribution coefficients of radiocaesium in soils and sediments. Part one: a simplified procedure for the solid phase characterisation

A comparative study is presented on the quantitative characterisation procedures of soils and sediments in terms of specific radiocaesium sorption potentials obtained during elaborate procedures, which include masking techniques, and a simplified protocol relying on a single K_D^137Csmeasurement. The elaborate and simple procedures were compared for some 120 soils and sediments of widely different origin, covering some three orders of magnitude in specific sorption capacities. The excellent agreement between both procedures provides the basis for a new and simple characterisation procedure which can be used in routine application.     

Mineralogical and chemical transformation of Oldoinyo Lengai natrocarbonatites, Tanzania

The minerals of Oldoinyo Lengai natrocarbonatite lavas are unstable under atmospheric conditions. Subsolidus mineral assemblages in natrocarbonatites were studied in 105 samples from contemporary eruptions ranging from present day to about 100 years old. The subsolidus minerals in natrocarbonatites were formed (i) along cracks on the lava surface from hot gases escaping during cooling, (ii) as atmospheric alteration by solution of water-soluble minerals, in particular halides and gregoryite, and by hydration of nyerereite under the influence of meteoric water and (iii) by reaction with fumarole gases. After solidification, the lavas were cut by a network of thin cracks, the edges of which are covered by polymineralic encrustations. Samples collected 2–24 h after eruption contain nahcolite, trona, sylvite, and halite with accessory kalicinite and villiaumite. Atmospheric humidity results immediately (≥ 2 h after eruption) in alteration of black lavas that is marked by the appearance of white powdery thermonatrite with nahcolite on the lava surface. Subsequent reaction (weeks, months, years) of natrocarbonatite with meteoric water and the atmosphere results in the formation of pirssonite, gaylussite, shortite, trona, thermonatrite, nahcolite and calcite. Generally, the first important step is the formation of pirssonite and the end-members are calcite carbonate rocks or loose aggregates. Fumarolic activity is common for the active northern crater of the volcano. Reaction of hot (54–141 °C) fumarolic gases with natrocarbonatite leads to the formation of sulphur, gypsum, calcite, anhydrite, monohydrocalcite, barite and celestine. Changes in mineralogy of the natrocarbonatite lead to substantial chemical transformation. The most obvious chemical changes in this process are the loss of Na, K, Cl and S, combined with an increase in H₂O, Ca, Sr, Ba, F and Mn. The oxygen and carbon isotopic composition of altered natrocarbonatites shows a significant shift from the primary “Lengai Box” to high values of δ¹⁸O and δ¹³C. Calcite exhibits δ¹³C values between − 2‰ and − 4‰ PDB and δ¹⁸O values of + 23‰ to + 26‰ SMOW. The observed assemblages of secondary minerals formed by reaction with atmosphere and meteoric water, the changes in chemical composition of the natrocarbonatite and field observations suggest that alteration of natrocarbonatite is an open-system low-temperature process. It takes place at temperatures between 8 and 43 °C with the addition of H₂O to the system and the removal of Na, K, Cl and S from the carbonatites. Low-temperature thermodynamic models developed for alkali carbonate systems can be used for the interpretation of Oldoinyo Lengai subsolidus mineralization.     

Political transformation,urban policy and the state in London's Docklands

The contemporary restructuring of urban space in the United Kingdom can be understood in terms of much broader social, political, and economic changes. This paper provides an analysis of this experience in London's Docklands, as a way of highlighting the connections between these social relations. We can best understand these changes by drawing upon regulation theory, which posits a firm, but dynamic, link between economic and political processes. Through an analysis of urban policy changes, political struggles, and economic shifts in London's Docklands, I argue for a more central role for the state and social movements in the understanding of social regulation and urban change. Finally, the paper considers the establishment of an Urban Development Corporation in the area in 1981, which represents an attempt by the central government to establish a new regime of economic and political life in the area. This has produced important conflicts at a local level, which typify the conflictual nature of attempts to restructure the economic and political relations of urban locales.     

27Al, 29Si,and 23Na MAS NMR study of an Al,Si ordered alkali feldspar solid solution series

Solid-state ²⁷Al, ²⁹Si and ²³Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and ²⁹Si NMR data have previously been reported. ²⁷Al δ_i vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the ²⁹Si chemical shifts assigned to the T2m-site. The ²⁷Al and ²⁹Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]¹b. The linewidths of the ²⁹Si and ²⁷Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average ²³Na δ_i varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average ²³Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution ²³Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the ²³Na NMR lineshape of Or49 after short periods of heat treatment indicate that ²³Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.     

The effects of quartz recrystallization and reaction on weak phase interconnection,strain localization and evolution of microstructure

We conducted axial compression and general shear experiments, at T = 900 °C and P = 1.5 GPa, on samples of banded iron formation (BIF) and synthetic aggregates of quartz, hematite and magnetite to investigate how dynamic recrystallization of quartz promotes strain localization, and the role of weak second phases (oxides) on the rheology and microstructural evolution of the aggregates. Experiments showed strain localization into oxide rich layers, and that the oxide content and oxide distribution are key factors for the strength of the aggregate. Only 2–10 wt.% hematite leads to pronounced weakening and increasing hematite content above ∼10% has only a minor additional effect. Where oxide grains are dispersed, the initial strength contrast with quartz induces stress concentrations at their tips, promoting high stress recrystallization-accommodated dislocation creep of quartz. Fine recrystallized quartz reacts with oxide, forming trails of fine reaction product (ferrosilite/fayalite) leading to the interconnection/percolation of a weaker matrix. The strength contrast between the quartz framework and these fine-grained trails promotes strain localization into micro-shear zones, inducing drastic strain weakening. Thus dynamic recrystallization of quartz promotes syn-deformational reactions leading to a microstructurally-controlled evolution of phase strength contrast. It results in a rheologic transition from load-bearing framework to a matrix-controlled rheology, with transition from S–C′ to S–C fabric with increasing strain.     

High pressure elasticity and phase transformation in brucite, Mg(OH)2

The first pressure derivatives of the second-order elastic constants have been calculated for brucite, Mg(OH)₂ from the second- and third-order elastic constants. The deformation theory and finite strain elasticity theory have been used to obtain the second- and third-order elastic constants of Mg(OH)₂ from the strain energy of the lattice. The strain energy ϕ is calculated by taking into account the interactions up to third nearest neighbors in the Mg(OH)₂ lattice. ϕ is then compared with the strain dependent lattice energy from continuum model approximation to obtain the expressions of elastic constants. The complete set of six second-order elastic constants C _IJ of brucite exhibits large anisotropy. Since C ₃₃ (= 21.6 GPa), which corresponds to the strength of the material along the c-axis direction, is less than the longitudinal mode C ₁₁ (= 156.7 GPa), the interlayer binding forces are weaker than the binding forces along the basal plane of Mg(OH)₂. The 14 nonvanishing components of the third-order elastic constants, C _IJK , of brucite have been obtained. All the C _IJK of brucite are negative except the values of C ₁₁₄ (= 230.36 GPa), C ₁₂₄ (= 75.45 GPa) and C ₁₃₄ (= 36.98 GPa). The absolute values of the C _IJK are, in general, one order of magnitude greater than the C _IJ ’s in the Mg(OH)₂ system as usually expected for a crystalline material. To our knowledge, no previous data are available to compare the pressure derivatives of brucite. The pressure derivatives of the two components viz., C ₁₄ and C ₃₃ become negative indicating an elastic instability in brucite while under pressure. This may be related to the phase transition of brucite largely involving rearrangements of H atoms revealed in the Raman spectroscopic, powder neutron diffraction and synchrotron X-ray diffraction studies.     

The influence of the low-high quartz transformation on recrystallization and grain growth during contact metamorphism (Traversella intrusion, North Italy)

Recrystallization and grain growth of quartz occur only within 35 m of the contact. This limit of recrystallization and grain growth coincides with an inferred maximum temperature of 620 ± 20°C, which at about 6–7 km is the temperature for the low-high quartz transformation. The remarkable coincidence of the temperature of about 620°C for the beginning of recrystallization and grain growth with the transformation temperature of quartz is explained by the atomic displacement mechanism of the low-high quartz transformation. The already disordered structure of the grain boundary becomes even more distorted by the fluctuations of the SiO₄ tetrahedra during the low-high quartz transformation. This results in an increase of the number of atoms which are transferred from one grain into the grain boundary, and from the grain boundary to the other grain. A lowering of the activation energy for grain boundary migration results such that grain boundary migration becomes the most important process for recrystallization and grain growth.     

Dynamics and evolution of the deep mantle resulting from thermal,chemical, phase and melting effects

The core–mantle boundary (CMB) – the interface between the silicate mantle and liquid iron alloy outer core – is the most important boundary inside our planet, with processes occurring in the deep mantle above it playing a major role in the evolution of both the core and the mantle. The last decade has seen an astonishing improvement in our knowledge of this region due to improvements in seismological data and techniques for mapping both large- and small-scale structures, mineral physics discoveries such as post-perovskite and the iron spin transition, and dynamical modelling. The deep mantle is increasingly revealed as a very complex region characterised by large variations in temperature and composition, phase changes, melting (possibly at present and certainly in the past), and anisotropic structures. Here, some fundamentals of the relevant processes and uncertainties are reviewed in the context of long-term Earth evolution and how it has led to the observed present-day structures. Melting has been a dominant process in Earth's evolution. Several processes involving melting, some of which operated soon after Earth's formation and some of which operated throughout its history, have produced dense, iron rich material that has likely sunk to the deepest mantle to be incorporated into a heterogeneous basal mélange (BAM) that is now evident seismically as two large low-velocity regions under African and the Pacific, but was probably much larger in the past. This BAM modulates core heat flux, plume formation and the separation of different slab components, and may contain various trace-element cocktails required to explain geochemical observations. The geographical location of BAM material has, however, probably changed through Earth's history due to the inherent time-dependence of plate tectonics and continental cycles.     

Grain boundary diffusion of oxygen,potassium and calcium in natural and hot-pressed feldspar aggregates

 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (¹⁸O, ⁴¹K, ⁴²Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994     

The effect of water,pressure, and strain on Al/Si order-disorder kinetics in feldspar

The disordering kinetics of Al/Si in albite depend on how the samples are dried, and thus on the presence of trace amounts of water. The disordering rate increases with water content and confining pressure. At 10 kb the activation energy is about 67 kcal/mole compared to about 87 kcal/mole for samples disordered in air. Simultaneous plastic deformation increases the disordering rate and the effect is most pronounced below 900° C at 10^?6/s. Some albite ordering and microcline disordering experiments show similar kinetic behavior. These results are significant for interpreting the structural state and the high-temperature deformation of feldspars.     

Dating deformation using crushed alkali feldspar: 40Ar/39Ar geochronology of shear zones in the Wyangala Batholith,NSW, Australia

Diffusion parameters have been estimated for K-feldspar in and adjacent to mylonite shear zones in the Wyangala Batholith. The parameters obtained suggest that deformation during mylonitisation would have caused argon systematics to reset because diffusion distances were reduced by cataclasis, deformation and/or recrystallisation. However, the mineral lattice remained sufficiently retentive to allow subsequently produced radiogenic argon to be retained. ⁴⁰Ar/³⁹Ar geochronology is thus able to constrain operation of these biotite-grade ductile shear zones to the period from ca 380 Ma to ca 360 Ma, at the end of the Tabberabberan Orogeny.     

四川开江恐龙骨骼化石矿物组分分离和微量元素组合的研究

文章详述了恐龙骨骼化石矿物组分的化学分离方法,同时对开江恐龙骨骼化石样品进行了分离和中子活化分析,通过对测试结果进行生物地球化学的对比研究.发现恐龙骨骼化石中某些微量元素异常明显,并推断其中的砷(As)、铬(Cr)、铷(Rb)的高异常含量和锌(Zn)的低异常含量极有可能是导致开江恐龙动物群集群死亡的原因之一。     

Effects of citrate on the dissolution and transformation of biotite,analyzed by chemical and atomic force microscopy

The aim of this study was to investigate the dissolution and transformation characteristics of phyllosilicate under low molecular weight organic acids in the farmland environment (pH 4.0–8.0). Changes of dissolution and morphology of biotite were evaluated using chemical extraction experiments and in situ/ex situ atomic force microscopy (AFM) with fluids of citric acid (CA) solution at pH 4.0, 6.0, and 8.0. Results of extracting experiments show that CA solutions contributed to the release rate of potassium (K), silicon (Si), and aluminum (Al) from biotite relative to a control aqueous solution. In situ AFM observations indicate that the dissolution of biotite from the biotite (0 0 1) surface occurred on the terrace, segment, and fringe of pits, while new etch pits did not readily form on biotite (0 0 1) surfaces in aqueous solutions. However, dissolution rates of terraces can be greatly accelerated with the help of citrate. In pH 4.0 CA solution, 70 min dissolution reactions of biotite (0 0 1) surfaces result in more etch pits than in pH 6.0 and 8.0 solutions. In addition, the transformation of biotite occurred simultaneously with the dissolution process. Secondary coating was observed on the biotite (0 0 1) surface after 140 h of immersion in a weak acid environment. Thus, the protons have a dominant role in the dissolution process of biotite with organic (carboxyl) acting as a catalyst under acidic condition. Based on the theory of interactions on a water–mineral interface in a weak acid environment, dissolution of biotite starts from defect/kink sites on the surface, one layer by one layer, and develops along the [h k 0] direction. A secondary coating that forms on the biotite (0 0 1) surface may restrain the formation and growth of etch pits, whereas this process may have a positive role on the stability of soil structure during long-term soil management.