Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K₂O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K_0.29Na_0.19Pb_0.31Fe_2.66Al_0.22(SO₄)_1.65(PO₄)_0.31(AsO₄)_0.04(OH)_7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO₄ at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO₄)₂ and minor hematite. The decomposition products of NaFe(SO₄)₂ are hematite and Na₂SO₄. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a?=?7.315 Å and c?=?016.598 Å. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.     

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.     

The effect of composition,temperature and pressure on the stability of the 1Tc and 2M polytypes of sapphirine

Microprobe analyses and structural characterisation by means of transmission electron microscopy and powder X-ray diffraction are presented for a suite of natural and synthetic sapphirines. Most sapphirines appear to consist of intergrowths of the common 2M polytype with minor amounts of the 1Tc phase, although the converse situation is found in some cases. Attempts to correlate the structural state of the mineral with other factors reveal that: (i) There is no strong relationship between mean tetrahedral cation radius or mean octahedral cation radius and the preferred polytype. The Tschermak substitution M²⁺M⁴⁺-M³⁺M³⁺ does not appreciably influence the 1Tc-2M equilibrium, (ii) However, the total content and mean oxidation state of iron in sapphirine are important in this respect. Fe²⁺ stabilises the 2M phase, whereas Fe³⁺ stabilises the 1Tc phase. (iii) P-T estimates for the host rocks, and estimates for the conditions of sapphirine crystallisation, where obtainable, suggest that the 1Tc phase is stable at lower T and higher P than the 2M phase. Some quantitative constraints are inferred.     

Stable carbon isotope variations in northwest Europe during the last glacial–interglacial transition

Stable carbon isotope data that span part of the last glacial–interglacial transition (ca. 14-9 ka ¹⁴C BP; ca. 15–11 ka cal. BP), and which derive from organ-specific plant macrofossils recovered from two lake sediment profiles in the UK and one in Norway, are compared. The recorded temporal variations show similar trends, which, over a millennial time-scale appear to parallel the main drift in δ¹⁸O as determined for the GRIP ice-core. It is postulated that some smaller scale variations in the δ¹³C profiles may reflect the shorter term oscillations in δ¹⁸O values evident in the GRIP record, although this is less certain. Overall, however, the results suggest that stable carbon isotope measurements based on organ-specific terrestrial plant macrofossils may provide (i) a means for establishing correlations between terrestrial successions and (ii) additional paleoenvironmental information, as the apparent ‘shadowing’ of the GRIP record indicates a common forcing mechanism for both Greenland δ¹⁸O and northwest European δ¹³C variations. From the evidence available we suggest that the recorded δ¹³C variations reflect fluctuations in air temperature and/or changes in water vapour pressure in the atmosphere. © 1997 John Wiley & Sons, Ltd.     

TEM study of a special grain boundary in a synthetic K-feldspar bicrystal: Manebach Twin

 A monoclinic KAlSi₃O₈ feldspar Manebach twin boundary was synthesized by diffusion bonding and examined using high-resolution transmission electron microscopy. The sharp (001) twin boundary is straight and free of strain. The boundary width is smaller than d₀₀₁. There is no rigid body shift observed at the twin boundary, and the feldspar structure is arranged symmetrically across (001). The twin boundary structure consists of bridged tetrahedral crankshafts, which are characteristic of the feldspar lattice. The grain boundary structure is in good agreement with the geometrical model of Taylor et al. (1934). The grain boundary composition of K_1/2H_1/2AlSi₃O₈ differs from their model. Received: 13 February 2002 / Accepted: 24 December 2002 Acknowledgements We thank M. Rühle, S. Hutt, J. Mayer, A. Strecker and U. Salzberger at MPI, Stuttgart, for their support and valuable advice in preparing TEM sections of bicrystals.     

Silica depleted melting of pelites. Petrogenetic grid and application to the Susqueda Aureole, Spain

Metapelitic rocks in the low pressure contact metamorphic aureole around the Susqueda igneous complex, Spain show a number of features that make them an ideal testing ground for the modelling of silica‐undersaturated melting. Rocks in the aureole experienced localized depletion in silica by the segregation of quartz veins during a pre‐anatectic, regional cordierite‐andalusite grade metamorphic event. These rocks were then intruded by gabbroic to dioritic rocks of the Susqueda igneous complex that formed a migmatitic contact metamorphic aureole in the country rocks. This migmatisation event caused quartz‐saturated hornfels and restite formation in rocks that had experienced no quartz vein segregation in the previous regional metamorphic event, but silica‐undersaturated melting in those rocks that were previously depleted in silica. Silica‐undersaturated melting is investigated using a new petrogenetic P–T projection and equilibrium pseudosections calculated in the KFMASH and NCKFMASH systems, respectively. The grid considers quartz absent equilibria and a range of phases that form typically in silica‐undersaturated bulk compositions, for example corundum. It is shown that the quartz‐rich precursors in the Susqueda contact aureole produced about 10% melt during contact metamorphism. However, most of this melt was extracted leaving behind rocks with restitic bulk compositions and minor leucosome segregation. It is suggested that the melt mixed with the host igneous rocks causing an apparent magmatic zoning from diorite in the centre of the complex to tonalite at the margins. In contrast, the quartz‐poor precursors (from which the quartz veins segregated) melted in the silica‐undersaturated field producing a range of assemblages including peritectic corundum and spinel. Melting of the silica‐undersaturated rocks produced only negligible melt and no subsequent melt loss.     

Structure Function Analysis of Two-Scale Scalar Ramps. Part II: Ramp Characteristics and Surface Renewal Flux Estimation

Ramp features in the turbulent scalar field are associated with turbulent coherent structures, which dominate energy and mass fluxes in the atmospheric surface layer. Although finer scale ramp-like shapes embedded within larger scale ramp-like shapes can readily be perceived in turbulent scalar traces, their presence has largely been overlooked in the literature. We demonstrate the signature of more than one ramp scale in structure functions of the turbulent scalar field measured from above bare ground and two types of short plant canopies, using structure-function time lags ranging in scale from isotropic to larger than the characteristic coherent structures. Spectral analysis of structure functions was used to characterize different scales of turbulent structures. By expanding structure function analysis to include two ramp scales, we characterized the intermittency, duration, and surface renewal flux contribution of the smallest (i.e., Scale One) and the dominant (i.e., Scale Two) coherent structure scales. The frequencies of the coherent structure scales increase with mean wind shear, implying that both Scale One and Scale Two are shear-driven. The embedded Scale One turbulent structure scale is ineffectual in the surface-layer energy and mass transport process. The new method reported here for obtaining surface renewal-based scalar exchange works well over bare ground and short canopies under unstable conditions, effectively eliminating the α calibration for these conditions and forming the foundation for analysis over taller and more complex surfaces.     

Comparison of cell- and vertex-centered discretization methods for flow in a two-dimensional discrete-fracture–matrix system

Simulations of flow for a discrete-fracture model in fractured porous rocks have gradually become more practical, as a consequence of increased computer power and improved simulation and characterization techniques. Discrete-fracture models can be formulated in a lower-dimensional framework, where the fractures are modeled in a lower dimension than the matrix, or in an equi-dimensional form, where the fractures and the matrix have the same dimension.