Mineralogy and geochemistry of the Texeo Cu–Co mine site (NW Spain): screening tools for environmental assessment

The Cu–Co–Ni Texeo mine has been the most important source of Cu in NW Spain since Roman times and now, approximately 40,000 m³ of wastes from mine and metallurgical operations, containing average concentrations of 9,263 mg kg⁻¹ Cu, 1,100 mg kg⁻¹ As, 549 mg kg⁻¹ Co, and 840 mg kg⁻¹ Ni, remain on-site. Since the cessation of the activity, the abandoned works, facilities and waste piles have been posing a threat to the environment, derived from the release of toxic elements. In order to assess the potential environmental pollution caused by the mining operations, a sequential sampling strategy was undertaken in wastes, soil, surface and groundwater, and sediments. First, screening field tools were used to identify hotspots, before defining formal sampling strategies; so, in the areas where anomalies were detected in a first sampling stage, a second detailed sampling campaign was undertaken. Metal concentrations in the soils are highly above the local background, reaching up to 9,921 mg kg⁻¹ Cu, 1,373 mg kg⁻¹ As, 685 mg kg⁻¹ Co, and 1,040 mg kg⁻¹ Ni, among others. Copper concentrations downstream of the mine works reach values up to 1,869 μg l⁻¹ and 240 mg kg⁻¹ in surface water and stream sediments, respectively. Computer-based risk assessment for the site gives a carcinogenic risk associated with the presence of As in surface waters and soils, and a health risk for long exposures; so, trigger levels of these elements are high enough to warrant further investigation.     

Calculated Phase Relations in the System NCKFMASH (Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

Pyrite–anhydrite–magnetite–pyroxene-type deposits and coexisting hydrothermal fluids in Mesozoic volcanic basins, Yangtze River Valley, China

Anhydrite–pyrite–magnetite–pyroxene–type deposits occur in the Mesozoic volcanic areas of the Middle–Lower Yangtze Valley in China. These deposits are hosted in alkaline basaltic rocks, and are generally accompanied by melanocratic and leucocratic alteration zones, both of which are characterized by a distinct vertical zonation pattern. Investigation of these zones indicates that the chemical compositions of solid solutions and polymorphs of various minerals vary spatially in the alteration profile, upwards from the lowest level, and outwards from the center.Here we report a case study on the Luohe deposit. In the melanocratic-alteration zone, the composition of magnetite (including trace elements Ti, V, Mg, Mn), pyroxene (Mg, Fe²⁺, Fe³⁺, Al₂O₃), plagioclase (An_xAb_{1 − x}), pyrite (Co, Ni) and apatite (F, CeO₂ + Y₂O₃ + La₂O₃) changes with depth. The isotherms of hydrothermal fluids determined from fluid inclusion data, including homogenization temperature and salinity, also vary with depth.Activity diagrams were constructed from mineral and isotherm analysis to estimate the chemical constraints on the alteration-mineral assemblages and the coexisting hydrothermal solutions for the Na₂O–K₂O–CaO–MgO–FeO–Fe₂O₃–A1₂O₃–SiO₂–H₂SO₄–H₂S–HCI–H₂O system at 350 to 600 °C and 500 bars (50 MPa), assuming that the major alteration mineral assemblages along the profile reflect the nature of the coexisting hydrothermal solutions. The activity diagrams adopted the major minerals as buffers to fix the activities of the aqueous species in the system, simulating the physicochemical conditions of the magnetite–anhydrite–pyroxene equilibrium and of solid solutions of diopside–hedenbergite, grossular–andradite and anorthite–albite found in the profile.This study provides an approach to modeling the chemical constraints of coexisting fluids in ore-alteration zones based on field observations.     

Role of unbalanced slab resistive force in the 2004 off Sumatra mega-earthquake (<Emphasis Type="Italic">M</Emphasis><Subscript>w</Subscript> > 9.0) event

Present study addresses the role of major plate-driving forces, particularly the slab pull and slab resistive forces, for the generation of 26 December 2004 M _w > 9.0 off Sumatra megathrust earthquake. Major controls on the plate-driving forces are normally visualized through age, speed, and average dip of the slab during subduction. Wide variation in age, plate obliquity, stress obliquity, subduction rate, dip angle, and flexing depth of the subducting oceanic lithosphere between Andaman and Sumatra thus allowed us for quantitative evaluation of the slab pull (F _SP) and slab resistive (F _SR) forces in three well-defined sectors (I, II and III). Computed values of these forces in the three sectors: (1) F _SP = 1.29 × 10¹³ N/m, F _SR = 1.41 × 10¹³ N/m; sector I, (2) F _SP = 2.10 × 10¹³ N/m, F _SR = 1.13 × 10¹³ N/m; sector II, and (3) F _SP = 2.08 × 10¹³ N/m, F _SR = 2.72 × 10¹³ N/m; sector III clearly suggest a spatial variation of stress regime in the subducting oceanic lithosphere. Excess F _SR in sectors I and III are interpreted as the causative forces behind the triggering of major seismic energy bursts near Sumatra and Andaman on 26 December 2004. A gap of minimum seismic energy burst near Great Nicobar possibly was controlled by the excess of F _SP in sector II. This study further advocates that the cyclic stress, resulted from unbalanced component of slab resistive force, had a definite control on the occurrence of 2004 off Sumatra megathrust earthquake around the flexing zone of the subducting lithosphere.     

Discovery of Radiolarian Fossils from the Aiketik Group at the Western End of the South Tianshan Mountains of Chinaand Its Implications

The Aiketik Group, distributed at the western end of the South Tianshan Mountains, China, is an important lithostratigraphic unit involved in the South Tianshan orogen. It is separated from the adjacent rocks by faults. Generally, the geologists ascribed it to the Upper Carboniferous according to Pseudostaffella sp., Profusulinella sp. and Fusulinella sp. found from the limestone and sandy limestone of Aiketik. Our radiolarian fossils were obtained from the chert samples collected from the Haladaok section located at the upper Tuoshihan River. The fossils mainly include Albaillella undulata Deflandre, Albaillella paradoxa Deflandre, Albaillella sp. aff. A. paradoxa Deflandre, Albaillella sp. cf. A. deflandrei Gourmelon, Albaillella sp., Albaillella excelsa Ishiga, Kito and Imoto (?), Belowea variabilis (Ormiston et Lane), Callella cf. C. parvispinosa Won, Entactinia cf. E. tortispina Ormiston et Lane, Entactinia aff. E. tortispina Ormiston et Lane, Entactinia variospina Won, Entactinia sp., Eostylodicty     

Cervandonite-(Ce) in ores of the Berezitovoe deposit: Second finding in the world

The supposedly second finding of rare arsenosilicate cervandonite-(Ce) in the world is characterized. The mineral was recognized in the ore-bearing metasomatic rocks of the Berezitovoe gold-base metal deposit (Upper Priamurye, Russian Far East) in association with quartz, biotite, muscovite, orthoclase, garnet (almandine-spessartine), tourmaline, basic plagioclase, and sulfides. The cervandonite is represented by optically homogeneous and heterogeneous aggregates with visible crystals from 10 fum to 0.1–0.3 mm in size. Based on the microprobe analysis, the average chemical composition of the homogeneous cervandonite-(Ce) aggregates is as follows (wt %): Ce₂O₃ - 13.00, La₂O₃ - 5.70, Nd₂O₃ - 5.20, Pr₂O₃ - 1.41, Y₂O₃ - 0.77, Sm₂O₃ - 0.77, Eu₂O₃ - 0.23, Gd₂O₃ - 0.54, Dy₂O₃ - 0.31, ThO₂ - 1.12, UO₂ - 0.30, TiO₂ - 12.86, Al₂O₃ - 9.24, Fe₂O₃ - 8.93, FeO - 2.68, CaO - 0.14, SiO₂ - 19.98, As₂O₃ - 16.19. The comparative study of the cervandonite-(Ce) from the Berezitovoe deposit and the analogous minerals from the Alpine mica gneiss of Mt. Pizzo Cervandone (Central Alps) showed that the former mineral can be assigned to a new variety of cervandonite-(Ce) in terms of its compositional features. This variety is characterized by an ordered stoichiometric composition corresponding to the simpler theoretical formula (Ce,Nd,La)(Fe³⁺, Fe²⁺, Ti⁴⁺, Al)₃ (Si₂As³⁺)₃O₁₂.     

The effect of species diversity on metal adsorption onto bacteria

In this study, we measure proton, Pb, and Cd adsorption onto the bacteria Deinococcus radiodurans, Thermus thermophilus, Acidiphlium angustum, Flavobacterium aquatile, and Flavobacterium hibernum, and we calculate the thermodynamic stability constants for the important surface complexes. These bacterial species represent a wide genetic diversity of bacteria, and they occupy a wide range of habitats. All of the species, except for A. angustum, exhibit similar proton and metal uptake. The only species tested that exhibits significantly different protonation behavior is A. angustum, an acidophile that grows at significantly lower pH than the other species of this study. We demonstrate that a single, metal-specific, surface complexation model can be used to reasonably account for the acid/base and metal adsorption behaviors of each species. We use a four discrete site non-electrostatic model to describe the protonation of the bacterial functional groups, with averaged pK_a values of 3.1 ± 0.3, 4.8 ± 0.2, 6.7 ± 0.1, and 9.2 ± 0.3, and site concentrations of (1.0 ± 0.17) × 10⁻⁴, (9.0 ± 3.0) × 10⁻⁵, (4.6 ± 1.8) × 10⁻⁵, and (6.1 ± 2.3) × 10⁻⁵ mol of sites per gram wet mass of bacteria, respectively. Adsorption of Cd and Pb onto the bacteria can be accounted for by the formation of complexes with each of the bacterial surface sites. The average log stability constants for Cd complexes with Sites 1-4 are 2.4 ± 0.4, 3.2 ± 0.1, 4.4 ± 0.1, and 5.3 ± 0.1, respectively. The average log stability constants for Pb complexes with Sites 1-4 are 3.3 ± 0.2, 4.5 ± 0.3, 6.5 ± 0.1, and 7.9 ± 0.5, respectively. This study demonstrates that a wide range of bacteria exhibit similar proton and metal adsorption behaviors, and that a single set of averaged acidity constants, site concentrations, and stability constants for metal-bacterial surface complexes yields a reasonable model for the adsorption behavior of many of these species. The differences in adsorption behavior that we observed for A. angustum demonstrate that genetic differences do exist between the cell wall functional group chemistries of some bacterial species, and that significant exceptions to the typical bacterial adsorption behavior do exist.     

Compression studies of gibbsite and its high-pressure polymorph

Various X-ray diffraction methods have been applied to study the compression behavior of gibbsite, Al(OH)₃, in diamond cells at room temperature. A phase transformation was found to take place above 3 GPa where gibbsite started to convert to its high-pressure polymorph. The high-pressure (HP) phase is quenchable and coexists with gibbsite at the ambient conditions after being unloaded. This HP phase was identified as nordstrandite based on the diffraction patterns obtained at room pressure by angle dispersive and energy dispersive methods. On the basis of this structural interpretation, the bulk modulus of the two polymorphs, i.e., gibbsite and nordstrandite, could be determined as 85 ± 5 and 70 ± 5 GPa, respectively, by fitting a Birch-Murnaghan equation to the compression data, assuming their K_o ^′ as 4. Molar volume cross-over occurs at 2 GPa, above which the molar volume of nordstrandite is smaller than that of gibbsite. The differences in the molar volume and structure between the two polymorphs are not significant, which accounts for the irreversibility of the phase transition. In gibbsite, the axial compressibility behaves as c/c _o > a/a _o > b/b _o. This is due to the fact that the dioctahedral sheets along the c-axis are held by the relatively weak hydrogen bonding, which results in the greater compressibility along this direction. In nord- strandite, the axial compressibility is b/b _o > c/c _o > a/a _o, which can also be interpreted as resulting from the the existence of hydrogen bonds along the b-axis. Received: 28 September 1998 / Revised, accepted: 22 December 1998     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

Cretaceous stratigraphy and palaeoenvironments of the Southern Petén Basin, Guatemala

The Cretaceous deposits of the Southern Petén Basin, an oil-producing province, are located to the south of the Yucatan Platform and to the east of the Chiapas Carbonate Platform of Mexico. The succession in the southern part of this basin has been studied both in wells and at outcrop by microfacies analysis. It is composed of 5000 m of shallow marine carbonates and evaporites with a few thin layers of pelagic limestones rich in organic carbon and planktic foraminifera deposited during peak transgressions or maximum flooding. The sedimentation of this thick succession was not continuous, and the section is punctuated by subaerial erosional bounding surfaces and a single hardground which marks the final drowning of the carbonate platform during the late Maastrichtian. New age determinations have been obtained on the basis of planktic and benthic foraminifera from the Aptian to Santonian Cobán Formation, D, C, B and A Members. Cobán C (Albian) and B (Cenomanian) Members are the present oil reservoirs. The rudist and alveolinid limestones of late Campanian and Maastrichtian age referred to the Campur Formation in the Southern Petén Basin are here reassigned to the Angostura Formation, as recognized in the Chiapas area. The Actela Formation is defined here to encompass the limestone breccia deposits that occur at the Cretaceous–Tertiary boundary and extend into the Parvularugoglobigerina eugubina Zone of early Danian age. The D, C, B and A Members of the Cobán Formation and the Angostura Formation represent second order transgressive and regressive trends in a passive margin area where the deposits indicate a succession of various environments, including fluviatile, salinas, shallow marine carbonate platform, outer shelf and intrashelf basin. High subsidence rates, sea-level changes and tectonic uplift controlled the sedimentation.

Abstract

Les formations crétacées du sud-est du Bassin du Petén, région pétrolière du nord du Guatemala, sont situées au Sud du Yucatan et à l'Est du Chiapas au Mexique. Ces sédiments ont été étudiés à la fois dans deux puits et à l'affleurement par l'analyse des microfaciès. Cet ensemble sédimentaire est composé de 5000 m de carbonates de plate-forme de faible profondeur et d'évaporites, dans lesquels s'intercalent de minces couches de calcaires pélagiques riches en matière organique et en foraminifères planctoniques. Ces calcaires pélagiques se sont déposés lors des maximums de transgressions. La sédimentation de cette épaisse série n'est pas continue et est ponctuée par quelques surfaces d'érosion sub-aérienne et une surface durcie qui souligne l'ennoyage définitif de la plate-forme carbonatée au Maastrichtien terminal. De nouvelles datations ont été obtenues sur la formation Cobán et ses membres D, C, B et A qui s'étagent de l'Aptien au Santonien. Les membres C (albien) et B (cénomanien) constituent les réservoirs productifs. Les calcaires à rudistes et à alveolinidés du Campanien supérieur–Maastrichtien ont été appelés à tort au Petén formation Campur. Ils doivent, selon nous, être attribués à la formation Angostura comme au Chiapas voisin, où affleurent des faciès comparables et de même âge. Une nouvelle formation est créée (formation Actela) pour les brèches calcaires de la limite Crétacé–Tertiaire et de la Zone à Eugubina du Danien inférieur. Les membres D, C, B, A de la formation Cobán et la formation Angostura représentent des cycles transgressifs–régressifs de deuxième ordre. Sur cette marge passive du Petén, les dépôts correspondent à des environnements variés comme des terres émergées soumises à une altération karstique et à des dépôts fluviatiles, des salinas, des plates-formes carbonatées marines, des shelf externes et des bassins intra plate-forme. La sédimentation a été, ici, contrôlée par une forte vitesse de subsidence, les variations du niveau marin et des soulèvements tectoniques.     

Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.     

Relations between load and settlement of circular foundations on or in a dense sand expressed by a function of diameter and depth

When load acts on a circular foundation on or in a dense sand, average contact pressure on the lower surface of the foundation is q and settlement of the foundation is s. Diameter and depth of the foundation are B and D_f. When the sand, B and D_f are given, we can know the relation between q and s/B by, e.g. a loading test, i.e. the relation is determined by B and D_f for the sand. Using the results of numerical analyses, we express a relation between q and s/B up to s=0.1B by functions of a single variable which is a linear combination of B and D_f. Consequently when two foundations have different B's and different D_f's but have the same value of the variable, the relations are the same. Then we examine whether the functions can express the results of eleven tests of model foundations of wide range of B and/or D_f. In all the tests, the relations are expressed with sufficient accuracy. Copyright © 2005 John Wiley & Sons, Ltd.     

δ18O and δ13C in fossil shells of Radix sp. from the sediment succession of a dammed palaeo‐lake in the Yarlung Tsangpo valley,Tibet, China

A series of confirmed and suspected dammed palaeo‐lake sedimentary successions is scattered within the middle Yarlung Tsangpo valley in Tibet. However, the chronology, the genesis of the dam and its location, the water level of the dammed lake, the process of dam failure and the spatiotemporal relationships between the sedimentary successions remain controversial. Here, we focus on one sedimentary succession of the suspected dammed palaeo‐lake at Xigazê. We measured the grain‐size distribution, magnetic susceptibility, organic and inorganic carbon content, and δ¹³C_org and δ¹⁵N_total ratios of the sediments. In addition, we measured the δ¹⁸O_shell and δ¹³C_shell values of modern and fossil Radix sp. shells, and the δ¹⁸O_water and δ¹³C_DIC values of the ambient water with different hydrological regimes. The results indicate that the δ¹⁸O_shell values of modern Radix sp. and the δ¹⁸O_water of the ambient water body significantly depend on its hydrological status. In addition, a strong positive relationship was observed between δ¹⁸O_shell values of modern Radix sp. shells and the δ¹⁸O_water of the ambient water on the Tibetan Plateau. According to this correlation, the δ¹⁸O_water values of the palaeo‐water body are reconstructed using the δ¹⁸O_shell values of Radix sp. fossil shells in the Xigazê section. Further, based on the δ¹⁸O_shell values of fossil Radix sp., the reconstructed δ¹⁸O_water of the palaeo‐water body and the specific habitats of Radix sp., we infer that the sedimentary succession in the Xigazê broad valley was mainly formed within the backwater terminal zone of a dammed palaeo‐lake and that the elevation of the water level of the lake was approximately 3811 m a.s.l. AMS ¹⁴C dating indicates that the deposits of the dammed palaeo‐lake were formed at about 33–22 cal. ka BP. Finally, the presence of Radix sp. fossil shells within the Xigazê section suggests that Radix sp. survived the late Last Glacial Period on the Tibetan Plateau.     

Accumulation rates of Th-230, Pa-231, and some transition metals on the Bermuda Rise

Measurements of ²³⁸U, ²³⁴U, ²³⁰Th, ²³²Th, ²³¹Pa, Mn, Fe, Co, Ni, Cu, and Zn were made on 23 samples from core GPC-5, a 29-m giant piston core from a water depth of 4583 m on the northeastern Bermuda Rise (33°41.2′N, 57°36.9′W). This area is characterized by rapid deposition of sediment transported by abyssal currents. Unsupported ²³⁰Th and ²³¹Pa are present throughout the core but, because of large variations in the sedimentation rate, show marked departures from exponential decay with depth. The trend with depth of the ${}^{231}\text{Pa}{}_{\mathrm{ex}}{}^{230}\text{Th}{}_{\mathrm{ex}}$ ratio is consistent with the average accumulation rate of 36 cm/1000 y reported earlier on the basis of radiocarbon dating and CaCO₃ stratigraphy. When expressed on a carbonate-free basis, concentrations of Mn, Co, Ni, Cu, Zn, ²³⁰Th_ex, and ²³¹Pa_ex all show cyclic variations positively correlated with those of CaCO₃. The correlations can be explained by a model in which all of these constituents, including CaCO₃, are supplied to the sediments from the water column at a constant rate. Concentration variations are controlled mainly by varying inputs of terrigenous detritus, with low inputs occurring during interglacials and high inputs during glacials. Relationships between the metal and ²³⁰Th_ex concentrations permit estimates of the rates at which the metals are removed to the sediment by scavenging from the water column. The results, in μg/cm²-1000 y, are: 4300 ± 1100 for Mn, 46 ± 16 for Ni and 76 ± 26 for Cu. These rates are somewhat larger than ocean-wide averages estimated by other methods, and the absolute rate of ²³⁰Th accumulation in GPC-5 averages about nine times higher than production in the overlying water column. This part of the Bermuda Rise and similar bottom-current deposits may act as important accumulators of elements scavenged from seawater.     

Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.     

Theoretical phase relations involving cordierite and garnet in the system MgO-FeO-Al2O3-SiO2

Theoretical stability relations have been derived between the phases cordierite (Cd), garnet (Ga), hypersthene (Hy), olivine (Ol), sapphirine (Sa), spinel (Sp), sillimanite (Si) and quartz (Qz) in the system MgO-FeO-Al₂O₃-SiO₂. Natural rock data and experimental evidence suggest that the Mg/Mg+Fe²⁺ ratio (X) of coexisting ferromagnesian phases decreases as follows: X _Cd>X _Sa>X _Hy>X _Ol>X _Sp>X _Ga. By use of this information four stable invariant points are proposed involving the phases: Cd, Hy, Sa, Ga, Si, Qz; Cd, Sa, Ga, Sp, Si, Qz; Cd, Hy, Sa, Ga, Sp, Qz; Cd, Ga, Hy, Ol, Sp, Qz. All univariant curves in the system are nonterminal, representing the breakdown of a join rather than the stability limit of an individual phase. A detailed treatment of divariant equilibria involving two and three ferromagnesian solid solutions illustrates the potential of these equilibria as Pressure-Temperature indicators. Interactions between solid-solid reactions and dehydration reactions involving biotite in the system MgO-FeO-Al₂O₃-SiO₂-K₂O-H₂O have been graphically analysed. The addition of biotite to anhydrous divariant assemblages does not affect the composition of coexisting phases at constant P and T but can affect their relative proportions.     

Tourmaline from the rare-element Pinilla pegmatite, (Central Iberian Zone, Zamora, Spain): chemical variation and implications for pegmatitic evolution

Summary Tourmaline is an ubiquitous constituent in the Pinilla de Fermoselle rare-element pegmatite (Zamora, Spain), as well as in barren pegmatitic and quartz–tourmaline veins inside the associated leucogranite. The rare-element pegmatite shows internal zoning, evolving from a barren facies, in the lower border zone, in contact with the leucogranite, to a Li-rich facies in the upper border zone, close to the host-rocks.Tourmalines from the veins within the leucogranite have highest Mg contents, and belong to the schorl–dravite series. The tourmalines from the rare-element pegmatite mostly belong to the schorl–elbaite series, with chemical compositions within the range of the end-members, whereas the tourmalines associated with the most evolved zone in the pegmatite belong to the elbaite–rossmanite series. The broad compositional range shown by the tourmalines correlates quite well with the pegmatite zoning. The most plausible substitution mechanism for the chemical evolution of tourmalines during crystallization seems to be Mg_–1Fe²⁺₁, [X]_–1^YAl_–1^XNa_–1^YFe²⁺₁, for the foitite–schorl series; ^YFe²⁺_–3^YAl_1.5^YLi_1.5, for the schorl–elbaite vector; ^XNa_–1^YLi_–0.5[X]₁^YAl_0.5, for the elbaite–rossmanite series; and, (OH)₁F₁ for all the tourmalines except the pink elbaites. This chemical variation in tourmaline is consistent with a crystal fractionation model for the evolution of the Pinilla pegmatite.     

Gebirgsbewegungen in einem unter Gebirgsdruck stehenden Stollen

ZusammenfassungGebirgsbewegungen in einem unter Gebirgsdruck stehenden Stollen (Messungen während des Vortriebes und Folgerungen für die Wahl der Vortriebsmethode) Durch einfache Messungen der Gebirgsbewegungen beim Vortrieb und bei Auskleidungsarbeiten kann auch im druckhaften Gebirge die Sicherheit der gewählten Auskleidung überprüft werden. Die Meßergebnisse zeigen, daß die Gebirgsbewegung rasch nach dem Abschlag zum Abklingen kommt, wenn die Auskleidung so ausgeführt wird, daß sie baldmöglichst die Kräfte der Spannungsumlagerung aufnehmen kann. Ihre Auswirkung in die Tiefe des Berges bleibt dann sehr klein.Anhand der Messungen kann auch festgestellt werden, daß nach Abklingen der Gebirgsbewegung diese erneut auflebt, wenn ein darauffolgender Arbeitsgang das erreichte Gleichgewicht wieder stört. Hierbei ist insbesondere nachweisbar, daß jedes Untergraben der Ulmenfundamente besonders rasch einsetzende starke Bewegungen hervorruft. Auf die Einhaltung einer günstigen Stützlinie, insbesondere im Ulmenbereich, muß daher besonders geachtet werden.Die Auskleidung mit Spritzbeton, gegebenenfalls unter Verstärkung durch Stahlbögen oder Felsnägel, ist den Auskleidungen mit Holz- oder Stahlbogenzimmerung überlegen. Sie kann rasch nach dem Abschlag in Anpassung an die jeweiligen Gebirgsverhältnisse aufgebracht werden. Ein Rückbau ist unnötig. Die Einbeziehung in die Endauskleidung ist möglich. Durch rasches Aufbringen bleibt die Auflockerung im Berginneren gering, wodurch auch eine Einsparung an Injektionsgut bei den abschließenden Verpreßarbeiten erreicht wird.

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SummaryMeasuring of Rock Movement (during Driving) in a Tunnel Section Under Pressure, and Consequences Drawn for the Choice of Driving Methods The safety of the installed lining can be tested in compressional rock by means of simple measurements of the rock movement during driving and lining work. The measurements show that the rock movement dies away rapidly after napping. Its effect on the interior of the rock is small, if the lining is executed so that it can absorb the forces of stress redistributions as quickly as possible.Measurements show that, after the rock movement has died away, it may restart, if following working processes again disturb the achieved equilibrium. Above all it is seen that every undermining of the side wall foundations may produce strong movements which start particularly rapidly. Special attention must be paid to the establishment of a favourable line of pressure particularly within the side wall area.Lining with shot concrete, reinforced if necessary by steel arches or rock bolting, is superior to lining with wood or steel arch timbering. Shot concrete may be applied quickly after napping, depending on the conditions of the respective rock. Dismantling is not necessary. Incorporation into the final lining is possible. By means of rapid application any weakening of the inner part of the rock s held to a minimum; this results in an economy of grouting material at the final pressure grouting stage.

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RésuméMouvements et pressions de terrain autour d'une galerie Par de simples mesures de déplacements pendant l'avancement du tunnel et les travaux de revêtement on peut vérifier la sécurité du revêtement choisi même dans les terrains qui poussent.Les résultats de mesures montrent qu'après l'abatage les mouvements s'éteignent rapidement si le revêtement est exécuté de manière à supporter aussitôt que possible les efforts résultant de la décompression du massif. Son effet au sein du massif reste donc très minime.Grâce à ces mesures, on peut aussi établir qu'après extinction ces mouvements se développent à nouveau si une phase ultérieure du travail trouble l'équilibre. A ce sujet, il apparait particulièrement démonstratif que chaque reprise en sous-oeuvre des murs latéraux provoque avec une particulière rapidité de forts déplacements. On doit être spécialement attentif à cause de celà à conserver une ligne d'appui favorable, notamment dans la région des piédroits.Le revêtement en béton projeté, renforcé le cas échéant par des cintres métalliques ou des boulons, est d'une qualité supérieure à celle du blindage, en bois ou métallique.Il peut être mis en place peu de temps après l'abatage et adapté à chaque comportement du terrain; il n'a pas à être démonté; il peut être inclus dans le revêtement définitif. Par sa mise en oeuvre rapide il limite la dégradation du massif rocheux ce qui économise le coulis dans les derniers travaux d'injection.

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Vortrag, gehalten beim XIX. Geomechanik-Kolloquium im Oktober 1969 in Salzburg.

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Mit 11 Abbildungen