Röntgenuntersuchung der wasserfreien Sulfate der dreiwertigen Metalle Eisen,Chrom und Gallium

Zusammenfassung Wasserfreies Eisen(III)sulfat, Fe₂(SO₄)₃, existiert in zwei Modifikationen. Nach Einkristallaufnahmen kristallisiert die eine wahrscheinlich in Raumgruppe (a_rh=8,791±0,004 Å, =55°52±2; Z=2), die andere in Raumgruppe C _2h ⁵ –P2₁/n (a=8,296±0,002 Å, b=8,515±0,002 Å, c=11,60±0,002 Å, =90°30; Z=4). Von Cr₂(SO₄)₃ und Ga₂(SO₄)₃ konnten für die rhomboedrischen Modifikationen, die isotyp zu jener von Fe₂(SO₄)₃ sind, aus Pulveraufnahmen die Gitterkonstanten bestimmt werden.

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Summary Anhydrous iron(III)sulfate exists in two modifications. From single-crystal work, one of the modifications crystallizes probably in space group (a_rh=8.791±0.004 Å, =55°52±2; Z=2), whereas the other in space group C _2h ⁵ –P2₁/n (a=8.296±0.002 Å, b=8.515±0.002 Å, c=11.60±0,002 Å, =90°30; Z=4). The lattice constants of the rhombohedral modifications of Cr₂(SO₄)₃ and Ga₂(SO₄)₃, which are isomorphous with rhombohedral Fe₂(SO₄)₃, have been determined from powder photographs.

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.     

Phosphorus-rich topaz from fractionated granites (Podlesí, Czech Republic)

Summary A detailed electron microprobe study of P, F, Ge and Ga-contents in rock-forming topaz was performed on a suite of Variscan granites at Podlesí in the western Kruné Hory Mts., Czech Republic. Topaz crystals from the relatively less evolved biotite- and protolithionite granites display homogeneous cathodo-luminescence (CL) intensities, whereas topaz from the marginal pegmatite, highly fractionated zinnwaldite granite and greisens show intense oscillatory zoning. Phosphorus contents reach 1.15wt% P₂O₅ in topaz from the zinnwaldite granite. Many topaz crystals are distinctly zoned with a maximum P content in the transition zone between core and rim. Phosphorus is incorporated into the topaz lattice by berlinite substitution: Al³⁺+P⁵⁺=Si⁴⁺+Si⁴⁺. The majority of analysed topazes are highly saturated in F, reaching 90–97% of the theoretical maximum saturation. Topaz from the marginal pegmatite only reaches 87–90% of F-saturation. There is a positive correlation between P_topaz and P_{whole rock}, but no correlation between F_topaz and F_{whole rock}. No difference has been found in P and F contents between magmatic and the hydrothermal (=greisen stage) topaz. Contents of Ge and Ga vary from around the detection limit (50ppm) up to 200ppm Ge and 100ppm Ga, respectively.     

Mössbauer study of the thermal decomposition of lepidocrocite and characterization of the decomposition products

The lepidocrocite (-FeOOH) to maghemite (-Fe₂O₃), and the maghemite to hematite (-Fe₂O₃) transition temperatures have been monitored by TGA and DSC measurements for four initial -FeOOH samples with different particle sizes. The transition temperature of -FeOOH to -Fe₂O₃ and the size of the resulting particles were not affected by the particle size of the parent lepidocrocite. In contrast, the -Fe₂O₃ to -Fe₂O₃ transition temperature seems to depend on the amount of excess water molecules present in the parent lepidocrocite. Thirteen products obtained by heating for one hour at selected temperatures, were considered. Powder X-ray diffraction was used to qualify their composition and to determine their mean crystallite diameters. Transmission electron micrographs revealed the particle morphology. The Mössbauer spectra at 80 K and room temperature of the mixed and pure decomposition products generally had to be analyzed with a distribution of hyperfine fields and, where appropriate, with an additional quadrupole-splitting distribution. The Mössbauer spectra at variable temperature between 4.2 and 400 K of two single-phase -Fe₂O₃ samples with extremely small particles show the effect of superparamagnetism over a very broad temperature range. Only at the lowest temperatures (T55 K), two distributed components were resolved from the magnetically split spectra. In the external-field spectra the m_I=0 transitions have not vanished. This effect is an intrinsic property of the maghemite particles, indicating a strong spin canting with respect to the applied-field direction. The spectra are successfully reproduced using a bidimensional-distribution approach in which both the canting angle and the magnetic hyperfine field vary within certain intervals. The observed distributions are ascribed to the defect structure of the maghemites (unordered vacancy distribution on B-sites, large surface-to-bulk ratio, presence of OH^- groups). An important new finding is the correlation between the magnitude of the hyperfine field and the average canting angle for A-site ferric ions, whereas the B-site spins show a more uniform canting. The Mössbauer parameters of the two hematite samples with MCD₁₀₄ values of respectively 61.0 and 26.5 nm display a temperature variation which is very similar to that of small-particle hematites obtained from thermal decomposition of goethite. However, for a given MCD the Morin transition temperature for the latter samples is about 30 K lower. This has tentatively been ascribed to the different mechanisms of formation, presumably resulting in slightly larger lattice parameters for the hematite particles formed from goethite, thus shifting the Morin transition to lower temperatures.Senior Research Associate, National Fund for Scientific Research (Belgium)     

The role of CO2 in the genesis of olivine melilitite

The nature of the near-liquidus phases for a mantle-derived olivine melilitite composition have been determined at high pressure under dry conditions and with various water contents. Olivine and clinopyroxene occur on or near the liquidus and there are no conditions where orthopyroxene crystallizes in equilibrium with the olivine melilitite. We have determined the effect on the liquidus temperature and liquidus phases of substituting CO₂ for H₂O on a mole for mole basis at 30 kb, using olivine melilitite + 20 wt% H₂O at = 0 and = (CO₂)/(H₂+CO₂) (mole fraction) = 0.25, 0.5, 0.75 and 1.0 (i.e. olivine melilitite + 38 wt% CO₂). Experiments were buffered by the MH or NNO buffers. At 30 kb, CO₂ is only slightly less soluble than water for <0.5 as judged by the slight increase in liquidus temperature on mole-for-mole substitution of CO₂ for H₂O and at 30 kb, 1200° C, = = 0.5 the olivine melilitite contains 8.8 wt% H₂O and 21 wt% CO₂ in solution. For 1 the CO₂ saturated liquidus is depressed 70 ° C below the anhydrous liquidus and the magma dissolves approx. 17% CO₂ at 30kb, 1400 ° C, 1, 0. Infrared spectra of quenched glasses have absorption bands characteristic of CO ₃ ⁼ and OH- molecules and no evidence for HCO ₃ ^- . The effect of CO ₃ ⁼ molecules dissolved in the olivine melilitite at high pressure is to suppress the near-liquidus crystallization of olivine and clinopyroxene and bring orthopyroxene and garnet on to the liquidus. We infer that olivine melilitite magmas may be derived by equilibrium partial melting (<5%) of pyrolite at 30 kb, 1150–1200 ° C, provided that both H₂O and CO₂ are present in the source region in minor amounts. Preferred conditions are 0< <0.5, 0.5< <1, and at low oxygen fugacities (相似文献   

Magnetic properties of iron-rich oxisols

Four occurrences of highly magnetic soil in Brazil have been analysed with a view to identifying the magnetic minerals and quantifying the soil magnetization. Techniques used include X-ray diffraction, X-ray fluorescence and Mössbauer spectroscopy. This approach leads us to identify several ways that these soils, which have spontaneous magnetization in the range 1_s<35 j/t/kg,="" can="" come="">One soil, which forms on dolerite (19.6 wt% Fe₂O₃), is found to contain fully-oxidized titanomaghemite inherited from the parent rock. This oxide has a canted ferrimagnetic spin structure with _s=36 J/T/kg of sample. The three others, formed on very iron-rich rock (50–90 wt% Fe₂O₃), contain magnetite or maghemite as the magnetic species and in two cases the soil is more magnetic than the parent rock (largely composed of pure hematite).     

Magnetic properties of surface sediments as proxies of recent anthropogenic pollution in the Anllóns riverbed (NW Spain)

A study of surface sediments from the Anllóns riverbed (northwestern Spain) was conducted to assess the use of their magnetic properties as proxies of recent trace element contamination (i.e., As, Zn, Pb, Cr, Ni and Cu). Thermomagnetic curves, hysteresis parameters, specific magnetic susceptibility χ, frequency-dependent magnetic susceptibility κ _FD%, magnetic remanence and saturation isothermal remanent magnetization ratios (i.e., S and SIRM/χ) reveal the presence of mostly fine-grained magnetite and maghemite in these samples. The Tomlinson Pollution Load Index (PLI), as well as the magnetic parameters χ, κ _FD%, SIRM/χ and S-ratios, vary more or less in agreement to each other when they are sequentially arranged throughout a 30-km-long transect that goes from the town of Carballo to the river mouth in Ponteceso. From that profile, it is possible to identify an anomaly of χ that lies between two small peaks of the PLI and seems to define a contaminated area probably linked to a diffuse low-impact source of pollution. There is also a conspicuous peak of the PLI that is likely associated to a nearby gold mine. The variations of the κ _FD%’s along the transect are the ones that best reflect the changes in the PLI values, regardless of the level of contamination. This result suggests that adsorption is the main mechanism of trace elements removal by Fe oxides in these samples. Direct signal analyses, used to decompose the isothermal remanent magnetization curves, reveal the presence of four magnetic fractions, with varying relative concentrations all over the profile, namely single-domain magnetite, close to the superparamagnetic threshold (SD/SP) and/or maghemite (\(\log B_{1/2}\) ca 1.2), single-domain magnetite (\(\log B_{1/2}\) ca 2), hematite (\(\log B_{1/2}\) ca 2.5) and goethite (\(\log B_{1/2}\) ca 3.5). Integrating all the available information, it was sketched out a likely sequence of events that included magnetic minerals neoformation in parent soils, their subsequent chemical transformations and the contamination episodes that affected the region.     

Arsenic removal from aqueous solutions by mixed magnetite–maghemite nanoparticles

In this study, magnetite–maghemite nanoparticles were used to treat arsenic-contaminated water. X-ray photoelectron spectroscopy (XPS) studies showed the presence of arsenic on the surface of magnetite–maghemite nanoparticles. Theoretical multiplet analysis of the magnetite–maghemite mixture (Fe₃O₄-γFe₂O₃) reported 30.8% of maghemite and 69.2% of magnetite. The results show that redox reaction occurred on magnetite–maghemite mixture surface when arsenic was introduced. The study showed that, apart from pH, the removal of arsenic from contaminated water also depends on contact time and initial concentration of arsenic. Equilibrium was achieved in 3 h in the case of 2 mg/L of As(V) and As(III) concentrations at pH 6.5. The results further suggest that arsenic adsorption involved the formation of weak arsenic-iron oxide complexes at the magnetite–maghemite surface. In groundwater, arsenic adsorption capacity of magnetite–maghemite nanoparticles at room temperature, calculated from the Langmuir isotherm, was 80 μmol/g and Gibbs free energy (∆G⁰, kJ/mol) for arsenic removal was −35 kJ/mol, indicating the spontaneous nature of adsorption on magnetite–maghemite nanoparticles.     

Temperature dependence of the hyperfine parameters of maghemite and al-substituted maghemites

Synthetic aluminum-substituted maghemite samples, -(Al _y Fe_1-y )₂O₃ with y=0, 0.032, 0.058, 0.084, 0.106 and 0.151 have been studied by Mössbauer spectroscopy at 8 K and in the range 80 K to 475 K at steps of 25 K. The spectra have been analysed as a superposition of two sextets composed of asymmetrical Lorentzians. The A- and B-site isomer shifts were constrained as: _A=_B-0.12 mm/s. From the temperature dependence of _B it was possible to determine the characteristic Mössbauer temperature and the intrinsic shift. Both quantities clearly increase with increasing Al content, at least up to 10 mole%. The temperature dependence of the A-and B-sites hyperfine fields could be satisfactorily reproduced using the molecular-field theory assuming an antiparallel spin configuration. The exchange integrals were found as: J _AB =-25 K; J _AA =-18 K and J _BB = -3 K. The hyperfine fields show a crossing in the vicinity of 300 K as a result of the relatively strong A-A interaction. The Curie temperature for the non-substituted sample was calculated to be 930 K and decreases to 765 K for the sample with 15 mol% Al. The gradual decrease of the saturation value of the A-site hyperfine field with increasing Al substitution and the constancy of this quantity for the B sites, suggest that the Al cations occupy the B sites.Research Director, National Fund for Scientific Research, Belgium     

Geochemistry of magnetite and maghemite in soils in European Russia

A method is proposed for determining the proportions of soluble Fe oxides (magnetite, FeOFe₂O₃, and maghemite, γ-Fe₂O₃) based on the measured magnetic susceptibility before and after treatment of soil with the Tamm or Mehra-Jackson (DCB) reagents. The development of hydromorphism in steppe soils in Ciscausiaia is associated with an increase in the magnetite fraction and, consequently, the average magnetite: maghemite ratio increases from 0.8–0.9 to 1.1. In these soils, smectites facilitate magnetite oxidation to maghemite. Soddy-podzolic and dark humic soils in the Cis-Ural region are noted for low values of the magnetite: maghemite ratio (0.5 on average) due to maghemite predominance. Soils in the Cis-Ural region on cover red-earth clays inherit lithogenic Fe oxides: hematite and maghemite. Hydromorphism in humid environments in northern taiga is accompanied by a significant increase in the magnetite: maghemite ratio to 4–9. Some issues of Fe geochemistry in magnetite and maghemite are considered.     

Barioferrite BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>: A new mineral species of the magnetoplumbite group from the Haturim Formation in Israel

A new mineral barioferrite—a natural analogue of synthetic barium ferrite Ba Fe ₁₂ ³⁺ O₁₉—has been identified in the central part of a metamorphosed barite nodule in the rock of the Haturim Formation (Mottled Zone) on the southern slope of Mount Ye’elim in Israel. The mineral is associated with barite, calcite, magnetite, and maghemite and occurs as tiny platy crystals up to 3 × 15 × 15 μm and their irregular aggregates. Barioferrite is black with streaks of brown, and its luster is submetallic. Its Calculated density is 5.31 g/cm³. The mineral is brittle; cleavage is absent. IR absorption bands (cm^?1) are observed at 635 (shoulder), 582, 544, 433, and 405 (shoulder). Barioferrite is characterized by ferrimagnetic behavior. Under a microscope in reflected light, barioferrite is grayish white with brownish red internal reflections, the pleochroism is weak (from gray-white on R _o to gray-white with a brown tint on R _e), and the bireflectance is weak with distinct anisotropy. The reflectance values of R _o/R _e, % (λ, nm) are 24.51/22.80 (470), 24.17/22.25 (546), 23.65/21.68 (589), and 22.67/20.85 (650). The chemical composition (electron microprobe, wt %; the ranges are given in parentheses) is BaO 13.13 (12.5–13.8), Fe₂O₃ 86.47 (85.5–87.5), and 99.60 in total. The empirical formula is Ba_0.95Fe _12.03 ³⁺ O₁₉. Barioferrite is hexagonal with space group P6₃/mmc, a = 5.875 (3) Å, c = 23.137 (19) Å, V = 691.6 (5) ų, and Z = 2. The strongest lines of the X-ray powder diffraction pattern [d, Å, (I, 5) (hkl)] are 2.938(46) (110), 2.770(100) (107), 2.624 (84) (114, 200), 2.420(44) (203), 2.225(40) (205), and 1.627(56) (304, 2.0.11). The holotype specimen of barioferrite is deposited at the Mineralogical Museum of St. Petersburg State University; its catalogue number is 1/19436.     

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.     

Aluminous orthopyroxene: Order-disorder,thermodynamic properties,and petrologic implications

Orthopyroxene has two tetrahedral sites, designated A and B, and two octahedral sites, M1 and M2. Crystallographic studies of synthetic and natural orthopyroxenes (opx) suggest that the tetrahedral Al is ordered nearly completely in the B site, but the octahedral Al disorders between M1 and M2 sites with a preference for M1. If the aluminum avoidance principle is obeyed, then the tetrahedral Si-Al ordering limits the Al substitution in opx to 25 mol%, thus leading to an end-member stoichiometry of Mg₃Al₂Si₃O₁₂ instead of MgAl₂SiO₆.The enthalpy of formation of these two components has been deduced from the available phase equilibrium data. The thermodynamic properties of the opx solid solution approximates ideal solution behavior more closely when treated in terms of the components Mg₄Si₄O₁₂(QEn)-Mg₃Al₂Si₃O₁₂(Py) than when expressed in terms of the components Mg₂Si₂O₆-MgAl₂SiO₆. A model has been developed for the octahedral disordering of Al as function of temperature and composition. These data enable calculation of the configurational entropy and molar entropy of Al-opx; distinction has been made between the cases of completely random mixing of Al and Si in the tetrahedral B site, and of random mixing without violation of the aluminum avoidance principle. The second model yields entropy of the Mg₃Al₂Si₃O₁₂ end member which agrees almost exactly with the value derived from phase equilibrium data. The partial molal entropies of the Orthopyroxene components QEn and Py can be derived from these data; their implications with respect to the P-T slopes of Al₂O₃ isopleths for the equilibrium of Orthopyroxene with forsterite and spinel/garnet have been discussed.     

Nephelines and analcimes in some alkaline igneous rocks

The paper presents electron microprobe analyses of nephelines and analcimes in alkaline igneous rocks ranging from theralite and basanite to mugearite and tinguaite. With few exceptions, the nephelines are Si-rich types whose Qz (quartz) components exceed those defining the limits of excess SiO₂ in solid solution in the Ne-Ks-Qz-H₂O system at 700°C and 1 kbarP _{H 2 O}. Unlike the nephelines in the basanites which show only limited grain-to-grain compositional variation, those in theralites and tinguaites from the differentiated Square Top intrusion, New South Wales, and in a New Zealand tinguaite vary significantly in Ne (nepheline), Ks (kalsilite) and Qz, even within individual samples, and they also may be strongly zoned. The rims of zoned nephelines are enriched in Si and Fe³⁺, relative to core compositions. These zoning trends contrast with the composional trend of successive bulk nepheline fractions in the Square Top sequence theralite tinguaite whereby Qz decreases. The nephelines coexist with high-temperature alkali feldspars. In the Ne-Ks-Qz system they plot on the Ne side of the Barth compositional join defined by the omission solid solution series with end-members K₂Na₆Al₈Si₈O₃₂ (the Buerger ideal composition; Ne₇₅Ks₂₅ mol%) and ₂Na₆Al₂Si₁₀O₃₂ (=cavity cation vacancy). The compositions of most natural nephelines are restricted to the field defined by Ne and the Barth join, compositions more K-rich than the ideal composition being relatively rare. The compositions of nephelines on the Ne side of the join are controlled by a number of factors which include the physical conditions attending nepheline crystallization and the compositions of the alkaline hosts. Interstitial analcimes from the Square Top intrusion display extensive NaAlSi substitution and their compositions extend from analcime of natrolite composition to compositions slightly more Si-rich than ideal NaAlSi₂O₆. Groundmass analcimes in the basanites, mugearite and New Zealand tinguaite have relatively constant compositions which approach stoichiometric NaAlSi₂O₆. An unusually Si-rich deuteric analcime (60.2% SiO₂) is also present in vugs in the New Zealand tinguaite. Experimental and other evidence, includingP/T data defining the coexistence of analcime and silica-undersaturated silicate melt in the NaAlSiO₄-KAlSiO₄-SiO₂-H₂O system, and inferred solidus temperatures of the various hosts (they would have exceeded the stability range of analcime) preclude a primary magmatic origin for the interstitial and groundmass analcimes. These are interpreted as subsolidus phases produced by nepheline interaction with deuteric and/or hydrothermal fluids. Analyses of nephelines and their derivative analcimes indicate that the latter may form from both Si-rich and more Si-poor nephelines.     

The α-β phase transition in cristobalite,SiO2

Cristobalite, a high temperature phase of silica, SiO₂, undergoes a (metastable) first-order phase transition from a cubic, , to a tetragonal, P4₃2₁2 (or P4₁2₁2), structure at around 220° C. The cubic C9-type structure for -cristobalite (Wyckoff 1925) is improbable because of two stereochemically unfavorable features: a 180° Si-O-Si angle and an Si-O bond length of 1.54 Å, whereas the corresponding values in tetragonal -cristobalite are 146° and 1.609 Å respectively. The structure of the -phase is still controversial. To resolve this problem, a symmetry analysis of the (or P4₁2₁2) transition in cristobalite has been carried out based on the Landau formalism and projection operator methods. The starting point is the ideal cubic ( ) C9-type structure with the unit cell dimension a (7.432 Å) slightly larger than the known a dimension (7.195 Å at 205° C) of -cristobalite, such that the Si-O-Si angle is still 180°, but the Si-O bond length is 1.609 Å. The six-component order parameter driving the phase transition transforms according to the X₄ representation. The transition mechanism essentially involves a simultaneous translation and rotation of the silicate tetrahedra coupled along 110. A Landau free-energy expression is given as well as a listing of the three types of domains expected in -cristobalite from the transition. These domains are: (i) transformation twins from a loss of 3-fold axes, (ii) enantiomorphous twins from a loss of the inversion center, and (iii) antiphase domains from a loss of translation vectors 1/2 110 (FP). These domains are macroscopic and static in -cristobalite, and microscopic and dynamic in -cristobalite. The order parameter , couples with the strain components as ², which initiates the structural fluctuations, thereby causing the domain configurations to dynamically interchange in the -phase. Hence, the - cristobalite transition is a fluctuation-induced first-order transition and the -phase is a dynamic average of -type domains.     

The graphite-COH fluid equilibrium in P,T, f_{O_2 } space

The oxygen fugacity ( ) of a C-O-H fluid in equilibrium with graphite has been determined in the range 10–30 kbar by equilibrating solid -buffer assemblages in graphite capsules containing C-O-H fluid. By using different buffers (Fe_xO-Fe₃O₄, Ni-NiO, Co-CoO, Mo-MoO₂), the of the graphite-saturated fluid is bracketed within a narrow range. This technique produces a calibration for the imposed on a sample contained within a graphite capsule. To achieve a thermodynamically-invariant system at fixed P and T, the was imposed on the system with an external buffer and the double-capsule technique. The experiments were performed in solid-media, high pressure apparatus with 19 mm tale-pyrex assemblies. A series of experiments at 10, 15, 20, 25, and 30 kbar, 800–1600° C, with imposed by the Fe₂O₃-Fe₃O₄-H₂O equilibrium were conducted. The experimental results have been fitted to the following equation:

Hydrochemical characteristics and pollution potential of Uluova aquifers,Elazığ, Turkey

The study area is in the southeastern part of the city of Elaz between 38°17–38°43 latitudes and 38°36–39°07 longitudes. Formations of Paleozoic, Mesozoic and Cenozoic age comprise confined and unconfined aquifers. Unconfined aquifers are represented by Na-Cl and Na-HCO₃ type waters while confined aquifers are characterized by Ca-HCO₃, Mg-HCO₃ and Na-HCO₃ type waters. Due to sodium pollution, as a result of irrigation from waters of Hazar lake in the plain, as well as intense use of artificial fertilizer and improper storage of animal fertilizers, NH₄-N, NO₃-N and total PO₄-P pollution are detected in waters of the unconfined aquifer. Organic material contents in waters of well nos. S₂₇, S₂₉ and S₃₂ completed in the unconfined aquifer are above 3.5 mg/l of Turkish Standard Institute (TSE), (266) standard. In confined aquifers, total PO₄-P pollution in four wells and NH₄-N pollution in three wells were observed to be above the TSE (266) standard.     

A Raman spectroscopic study of Fe–Mg olivines

End-member synthetic fayalite and forsterite and a natural solid-solution crystal of composition (Mg_1.80,Fe_0.20)SiO₄ were investigated using Raman spectroscopy. Polarized single-crystal spectra were measured as a function of temperature. In addition, polycrystalline forsterite and fayalite, isotopically enriched in ²⁶Mg and ⁵⁷Fe, respectively, were synthesized and their powder spectra measured. The high-wavenumber modes in olivine consist of internal SiO₄ vibrations that show little variation upon isotopic substitution. This confirms conclusions from previous spectroscopic studies that showed that the internal SiO₄ vibrations have minimal coupling with the lower-wavenumber lattice modes. The lowest wavenumber modes in both forsterite and fayalite shift in energy following isotopic substitution, but with energies less than that which would be associated with pure Mg and Fe translations. The low-wavenumber Raman modes in olivine are best described as lattice modes consisting to a large degree of mixed vibrations of M(2) cation translations and external vibrations of the SiO₄ tetrahedra. The single-crystal spectra of forsterite and Fo₉₀Fa₁₀ were recorded at a number of temperatures from room temperature to about 1200 °C. From these data the microscopic Grüneisen parameters for three different A_g modes for both compositions were calculated, and also the structural state of the solid solution crystal was investigated. Small discontinuities observed in the wavenumber behavior of a low-energy mixed Mg/T(SiO₄) mode between 700 and 1000 °C may be related to minor variations in the Fe–Mg intracrystalline partitioning state in the Fo₉₀Fa₁₀ crystal, but further spectroscopic work is needed to clarify and quantify this issue. The mode wavenumber and intensity behavior of internal SiO₄ vibrations as a function of temperature are discussed in terms of crystal field and dynamic splitting and also ₁ and ₃ coupling. Crystal-field splitting increases only very slightly with temperature, whereas dynamical-field splitting is temperature dependent. The degree of ₁–₃ coupling decreases with increasing temperature.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written: