Phase transition in K2Cd2(SO4)3: Order parameter and microscopic distortions

The transition from P2₁3(T ⁴) to P2₁2₁2₁(D ₂ ⁴ ) in the langbeinite K₂Cd₂(SO₄)₃ has been analyzed using group theoretical methods and previously published structural data above and below the transition. We find that because the transition is strongly first-order, the primary-order parameter has relatively large values at the transition temperature, and higher order terms which involve the order parameter, the strain, and the coupling of the two must be included in the Landau expansion for the free energy. Complex displacements occur at the transition for all atoms of the unit cell, but these displacements can be resolved into contributions which can be shown from symmetry considerations to transform as the _{2 3} irrep of P2 ₁ 3(T ⁴) as well as contributions from symmetry-preserving displacements which transform under the irrep ₁. Therefore, the transition is not a simple one and involves sulfate rotations and cadmium and potassium ion displacements.     

Modes of occurrence of mercury and other trace elements in coals from the warrior field, Black Warrior Basin, Northwestern Alabama

The mineralogic residence and abundance of trace metals is an important environmental issue. Data from the USGS coal quality database show that potentially toxic elements, including Hg, As, Mo, Se, Cu, and Tl are enriched in a subset of coal samples in the Black Warrior Basin of Alabama, USA. Although the coal as-mined typically is low in these elements, localized enrichments occur in high-pyrite coals and near faults. Microscopic analyses demonstrate that the residence of these elements is dominantly in a late-stage pyrite associated with structurally disrupted coal. Further, our data suggest addition of Hg to the coal matrix as well. The source of these trace elements was hydrothermal fluids driven into the Black Warrior Basin by Alleghanian age tectonism.     

Phase transitions in leucite,KAISi2O6

An order parameter treatment of the phase transitions in leucite, KAlSi₂O₆, at approximately 950 and 920 K: (cubic) I4₁ acd(tetragonal) I4₁ a(tetragonal) is presented in terms of Landau theory and induced representation theory. The Al-Si order with decreasing temperature is taken as the primary order parameter to which other distortions (K⁺ ion displacements, strain components, etc.) couple linearly. The expected Al-Si ordering behavior and the associated K⁺ ion displacements for both transitions are derived and the resulting twin domain orientations are listed. The sequence of phase transitions results from a coupling of ₃ ⁺ and ₄ ⁺ representations. The Landau free energy for the five-dimensional reducible representation has been simplified to two components resulting in a linearquadratic coupling of the components. Possible phase diagrams are derived by free energy minimization. The cubic tetragonal transition is first-order, whereas the tetragonal-tetragonal transition may be second order. A tricritical point exists at which the first-order transition changes to second-order.     

A dynamical model for the I\bar 1 - P\bar 1 phase transition in anorthite,CaAl2Si2O8

The non-ferroic triclinic to triclinic \(I\bar 1 - P\bar 1\) phase transition in anorthite is described in terms of the spontaneous onset of an order parameter η. A triclinic to triclinic phase transition can be driven by order parameters (representations) arising from the Γ, Z, X, U, V, R, Y, and T points of symmetry of the Brillouin zone. Each point leads to a set of two inequivalent representations and thus there is a total of sixteen inequivalent order parameters. However, only the R ₁ ⁺ representation is consistent with the change from the body-centered to primitive cell (increase of primitive cell size of two) and also with the origin of the two space groups (inversion center) being at the same position. The R ₁ ⁺ order parameter of the high symmetry triclinic phase \(P\bar 1_0\) (or equivalently \(I\bar 1\) ) causes a reciprocal lattice change and, in terms of the lower symmetry reciprocal lattice, the order parameter corresponds to the b^* point. This is consistent with experimentally observed x-ray diffuse scattering. Using induced representation theory, microscopic distortions compatible with the R ₁ ⁺ order parameter are obtained. Assuming a distortion in an arbitrary direction at the general 2(i) Wyckoff position (x₀,y₀,z₀) of \(P\bar 1_0\) (the higher symmetry phase) induced representation theory demands an opposite displacement at the position (x₀, y₀, z₀), an opposite displacement at (x₀+1,y₀+1,z₀+1), and the same displacement at ( \(\bar x\) ₀+1, \(\bar y\) ₀+1, \(\bar z\) ₀+1) of \(P\bar 1_0\) . This is also consistent with experiment. The presence of the weak c-type reflections above the transition is attributed to the fluctuating lower symmetry antiphase domains related by the translation (1/2, 1/2, 1/2).     

The α-β phase transition in AlPO4 cristobalite: Symmetry analysis,domain structure and transition dynamics

Despite their crystallographic differences, the mechanisms of the α-β phase transitions in the cristobalite phases of SiO₂ and AlPO₄ are very similar. The β→α transition in AlPO₄ cristobalite is from cubic ( $\left( {F\bar 43m} \right)$ ) to orthorhombic (C222₁), whereas that in SiO₂ cristobalite is from cubic ( $\left( {Fd\bar 3m} \right)$ ) to tetragonal (P4₃2₁2 or P4₁2₁2). These crystallographic differences stem from the fact that there are two distinct cation positions in AlPO₄ cristobalite as opposed to one in SiO₂ cristobalite and the ordered (Al,P) distribution is retained through the phase transition. As a result, there are significant differences in their crystal structures, domain configurations resulting from the phase transition and Landau free energy expressions. A symmetry analysis of the “improper ferroelastic” transition from $F\bar 43m \to C222_1$ in AlPO₄ cristobalite has been carried out based on the Landau formalism and the projection operator methods. The six-component order parameter, η driving the phase transition transforms as the X₅ representation of $F\bar 43m$ and corresponds to the simultaneous translation and rotation of the [AlO₄] and [PO₄] tetrahedra coupled along 110. The Landau free energy expression contains a third order invariant, the minimization of which requires a first-order transition, consistent with experimental results. The tetrahedral configurations of twelve α phase domains resulting from the β→α transition in AlPO₄ cristobalite are of two types: (1) transformation twins from a loss of the 3-fold axis, and (2) antiphase domains from the loss of the translation vectors 1/2[101] and 1/2[011] (F→C). In contrast to α-SiO₂ cristobalite, the α-AlPO₄ cristobalite (C222₁) does not have chiral elements (4₃, 4₁) and hence, enantiomorphous domains are absent. These transformation domains are essentially macroscopic and static in the α phase and microscopic and dynamic in the β phase. The order parameter, η couples with the strain components, which initiates the structural fluctuations causing the domain configurations to dynamically interchange in the β phase. An analysis of the MAS NMR data (²⁹Si, ¹⁷O, ²⁷Al) on the α α-β transitions in SiO₂ and AlPO₄ cristobalites (Spearing et al. 1992, Phillips et al. 1993) essentially confirms the dynamical model proposed earlier for SiO₂ cristobalite (Hatch and Ghose 1991) and yields a detailed picture of the transition dynamics. In both cases, small atomic clusters with the configuration of the low temperature α phase persist considerably above the transition temperature, T₀. The NMR data on the β phases above T₀ cannot be explained by a softening of the tetrahedral rotational and translational modes alone, but require the onset of an order-disorder mechanism resulting in a dynamic averaging due to rapidly changing domain configurations considerably below T₀.     

A Petroleum System for the Salina Basin in Kansas Based on Organic Geochemistry and Geologic Analog

The Salina Basin historically has been an exploration desert—a home of dryholes. Although this basin, which underlies much of north-central Kansas, may never be a prolific source of hydrocarbons, recent research into the maturation and geochemistry of organic matter and oils in Kansas can provide guidelines for a new exploration strategy. The Salina Basin is similar to the oil-productive Forest City Basin in northeastern Kansas in many ways. Both basins originated as a single large basin (i.e., the North Kansas Basin) prior to the rise of the Nemaha Uplift in Late Mississippian-Early Pennsylvanian time. Their Paleozoic stratigraphy thus is similar and the axes of both basins are presently at approximately the same depth. Thermal maturation modeling and available organic-matter maturation data indicate that the lower Paleozoic rocks in the axes of both basins are in the early stages of oil generation. In the Forest City Basin the Ordovician Simpson Group is the deepest known hydrocarbon source-rock—oil-reservoir interval, and by analogy, exploration tests in the Salina Basin, at a minimum, should penetrate through this stratigraphic interval. Ordovician Simpson Group shales in the Forest City Basin are the source rocks for a geochemically distinct oil, which also occurs in Ordovician reservoirs in the extreme southern end of the Salina Basin. To increase the odds of success in an exploration program in the Salina Basin, wildcat wells should be drilled where thermal maturation is greatest. The broad NW–SE-trending basin axis is the most logical area. Exploration tests along this axis in the northern end of the basin may have an extra advantage as organic matter in the Simpson Group may be more thermally mature because of greater burial depth during the Cretaceous. Along the eastern margin of the nearby Central Kansas Uplift and Pratt Anticline, several Paleozoic geologic structures, some of which contain major oil fields, are attributable to tectonic reactivation along the western margin of the Precambrian Central North American Rift System (CNARS). Prospective structural trends in the Paleozoic section of the Salina Basin are anticipated to be associated with this underlying tectonic boundary. The western margin of the CNARS trends NNE–SSW where it passes under the axis of the Salina Basin in northeastern Lincoln and southeastern Mitchell counties. This area is sparsely drilled, with less than two tests per township. If an exploration program can define lower Paleozoic structural closures in this region, these structures may represent the best chance for future petroleum discoveries.     

Environmental and cultural changes in highland Guatemala inferred from Lake Amatitlán sediments

We inferred the late Holocene environmental history of the Guatemala highlands from multiple lines of evidence in a sediment core from Lake Amatitlán. Inferred environmental changes are generally synchronous with archaeologically documented highland Maya cultural shifts. Population increases in the Middle Preclassic, Early Classic, and Late Postclassic are associated with deforestation and soil erosion. Land abandonment in the Late Preclassic, Late Classic, and Early Postclassic is associated with evidence for reforestation and soil stabilization. Diatoms indicate relatively lower lake level and greater trophic status at times of reduced human impact, from ca. 250 B.C. to A.D. 125 and from ca. A.D. 875 to 1375. Decreased water levels were probably due to drier climate, to reforestation, or both. Lake eutrophication was caused by reduced water volume combined with a legacy of long‐term agricultural activity. Our data contribute to the understanding of relations among ancient Maya culture, climate, and environment. © 2011 Wiley Periodicals, Inc.     

Early Ipswichian (last interglacial) sea level rise in the channel region: Stone Point Site of Special Scientific Interest,Hampshire, England

Constraining the speed of sea level rise at the start of an interglacial is important to understanding the size of the ‘window of opportunity’ available for hominin migration. This is particularly important during the last interglacial when there is no evidence for significant hominin occupation anywhere in Britain. There are very few finer grained fossiliferous sequences in the Channel region that can be used to constrain sea level rise and they are preserved only to the north of the Channel, in England. Of these, the sequence at Stone Point SSSI is by far the most complete. Data from this sequence has been previously reported, and discussed at a Quaternary Research Association Field Meeting, where a number of further questions were raised that necessitated further data generation. In this paper, we report new data from this sequence – thin section analysis, isotopic determinations on ostracod shells, new Optical Stimulated Luminescence ages and Amino Acid Recem analyses. These show early sea level rise in this sequence, starting during the pre-temperate vegetation zone IpI, but no early warming. The implications of this almost certainly last interglacial sequence for the human colonisation of Britain and our understanding of the stratigraphic relationship of interglacial estuarine deposits with their related fluvial terrace sequences is explored.