Stable isotope (C,O, S) systematics of the mercury mineralization at Idrija,Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the ¹³C and ¹⁸O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the ¹³C and ¹⁸O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (¹³C–4 and ¹⁸O+10), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The ³⁴S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The ³⁴S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from –19.1 to +22.8, and from –22.4 to +59.6, respectively, suggesting mixing of sulfur from different sources. The peak of ³⁴S values of cinnabar and pyrite close to 0 is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the ³⁴S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive ³⁴S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.Editorial handling: P. Lattanzi     

Composite synvolcanic intrusions associated with Precambrian VMS-related hydrothermal systems

Large subvolcanic intrusions are recognized within most Precambrian VMS camps. Of these, 80% are quartz diorite–tonalite–trondhjemite composite intrusions. The VMS camps spatially associated with composite intrusions account for >90% of the aggregate sulfide tonnage of all the Precambrian, intrusion-related VMS camps. These low-alumina, low-K, and high-Na composite intrusions contain early phases of quartz diorite and tonalite, followed by more voluminous trondhjemite. They have a high proportion of high silica (>74% SiO ₂) trondhjemite which is compositionally similar to the VMS-hosting rhyolites within the volcanic host-rock successions. The quartz-diorite and possibly tonalite phases follow tholeiitic fractionation trends whereas the trondhjemites fall within the composition field for primitive crustal melts. These transitional M-I-type primitive intrusive suites are associated with extensional regimes within oceanic-arc environments. Subvolcanic composite intrusions related to the Archean Sturgeon Lake and Noranda, and Paleoproterozoic Snow Lake VMS camps range in volume from 300 to 1,000 km ³. Three have a sill morphology with strike lengths between 15 and 22 km and an average thickness between 1,500 and 2,000 m. The fourth has a gross stock-like shape. The VMS deposits are principally restricted to the volcanic strata above the strike length of the intrusions, as are areally extensive, thin exhalite units. The composite intrusions contain numerous internal phases which are commonly clustered within certain parts of the composite intrusion. These clusters underlie eruptive centers surrounded by areas of hydrothermal alteration and which contain most of the VMS deposits. Early quartz-diorite and tonalite phases appear to have intruded in rapid succession. Evidence includes gradational contacts, magma mixing and disequilibrium textures. They appear to have been emplaced as sill-dike swarms. These early phases are present as pendants and xenoliths within later trondhjemite phases. The trondhjemite phases contain numerous internal contacts indicating emplacement as composite sills. Common structural features of the composite intrusions include early xenolith phases, abundant small comagmatic dikes, fractures and veins and, in places, columnar jointing. Internal phases may differ greatly in texture from fine- to coarse-grained, aphyric and granophyric through seriate to porphyritic. Mineralogical and isotopic evidence indicates that early phases of each composite intrusion are affected by pervasive to fracture-controlled high-temperature (350–450 °C) alteration reflecting seawater-rock interaction. Trondhjemite phases contain hydrothermal-magmatic alteration assemblages within miarolitic cavities, hydrothermal breccias and veins. This hydrothermal-magmatic alteration may, in part, be inherited from previously altered wall rocks. Two of the four intrusions are host to Cu-Mo-rich intrusive breccias and porphyry-type mineralization which formed as much as 14 Ma after the main subvolcanic magmatic activity. The recognition of these Precambrian, subvolcanic composite intrusions is important for greenfields VMS exploration, as they define the location of thermal corridors within extensional oceanic-arc regimes which have the greatest potential for significant VMS mineralization. The VMS mineralization may occur for 2,000 m above the intrusions. In some cases, VMS mineralization has been truncated or enveloped by late trondhjemite phases of the composite intrusions. Evidence that much of the trondhjemitic magmatism postdates the principal VMS activity is a critical factor when developing heat and fluid flow models for these subseafloor magmatic-hydrothermal systems.     

Regional-scale hydrothermal alteration in the Central Blake River Group,western Abitibi subprovince,Canada: implications for VMS prospectivity

The Late Archean Blake River Group is a thick succession of predominantly mafic volcanic rocks within the southern zone of the Abitibi greenstone belt. It contains a number of silicic volcanic centers of different size, including the large Noranda volcanic complex, which is host to 17 past-producing volcanogenic massive sulfide deposits. The Noranda complex consists of a 7- to 9-km-thick succession of bimodal mafic and felsic volcanic rocks erupted during five major cycles of volcanism. Massive sulfide formation coincided with a period of intense magmatic activity (cycle III) and the formation of the Noranda cauldron. Hydrothermal alteration in these rocks is interpreted to reflect large-scale hydrothermal fluid flow associated with rapid crustal extension and rifting of the volcanic complex. The alteration includes abundant albite, chlorite, epidote and quartz (silicification), which exhibit broad stratigraphic and structural control and correlate with previously mapped whole-rock oxygen isotope zonation. The Mine Sequence volcanic rocks are characterized by abundant iron-rich chlorite (Fe/Fe+Mg >0.5), hydrothermal amphibole (ferroactinolite) and coarse-grained epidote of clinozoisite composition (<10 wt% Fe ₂O ₃). Volcanic rocks of the pre-cauldron sequences, which contain only subeconomic stringer mineralization, are characterized by less abundant chlorite and mainly fine-grained epidote (>10 wt% Fe ₂O ₃) lacking the clinozoisite solid solution. Alteration in the Mine Sequence volcanic rocks persists along strike well beyond the limits of the main ore deposits (as far as several tens of kilometers) and can be readily distinguished from greenschist facies metamorphic assemblages at a regional scale. The lack of similar alteration in the pre-cauldron sequences is consistent with limited ¹⁸O-depletion and suggests that the early history of the volcanic complex did not support large-scale, high-temperature fluid flow in these rocks. Comparisons with a much smaller, barren volcanic complex in nearby Ben Nevis township reveal important differences in the alteration mineralogy between volcanoes of different size, with implications for area selection during regional-scale mineral exploration. The Ben Nevis Complex consists of a 3- to 4-km-thick succession of mafic, intermediate and felsic volcanic rocks centered on a small subvolcanic intrusion. Alteration of the volcanic rocks comprises mainly low-temperature assemblages of prehnite, pumpellyite, magnesium-rich chlorite (Fe/Fe+Mg <0.5), iron-rich epidote (>10 wt% Fe ₂O ₃) and calcite. Actinolite ± magnetite alteration occurs proximal to the intrusive core of the complex, but the limited extent of this alteration indicates only local high-temperature fluid circulation adjacent to the intrusion. A distal zone of carbonate alteration is located 4–6 km from the center of the volcano. Although iron-bearing carbonates are present locally within this zone, the absence of siderite argues against a high-temperature origin for this alteration. These observations do not offer positive encouragement for the existence of a fossil geothermal system of sufficient size or intensity to have produced a large massive sulfide deposit.     

Crystal chemistry of some Mg,Cr, V normal spinels from Sludyanka (Lake Baikal,Russia): the influence of V<Superscript>3+</Superscript> on structural stability

A suite of vanadian magnesiochromites from the Sludyanka metamorphic complex (South Lake Baikal, Russia) were investigated by means of X-ray single-crystal structural refinements and microprobe analyses. Various morphological types of Cr–V-bearing Mg spinels are located in calc–silicate metamorphic rocks, in an assemblage that also contains other Cr–V minerals such as escolaite–karelianite, uvarovite–goldmanite, Cr–V-bearing clinopyroxene, tourmaline, amphibole, mica, etc. Along the suite there is widespread V–Cr substitution (0.14 V³⁺ 0.95 afu, 1.02 Cr³⁺ 1.80 afu), and minor, variable Al contents. The Mg content of slightly lesser than 1 afu, is almost constant. Cell parameters and octahedral bond distances increase with V³⁺. Unexpectedly, the Mg–O tetrahedral bond distance also increases slowly with V³⁺. This weak dragging effect contributes towards maintaining distortion of the oxygen array with respect to the ideal CCP, thus providing a shielding effect, which reduces V³⁺–V³⁺ repulsion. This leads to the energetic stabilization of the structure, in spite of the increase of bond strain with increasing V³⁺ contents.     

High-temperature X-ray investigation of natural columbites

Structural investigations at high temperature were carried out on natural columbite samples across the join Fe(Nb_0.95Ta_0.05)₂O₆–Mn(Nb_0.95Ta_0.05)₂O₆. The samples were preliminarily annealed to attain the complete cation-ordered state and avoid the superimposition of the effects of cation ordering during high-temperature studies. Unit-cell parameters of three columbites with different X_Fe content were measured at regular intervals in the temperature range 25–900 °C using single-crystal X-ray diffraction techniques. The crystal structures of completely ordered ferrocolumbite and manganocolumbite were also refined from intensity data collected at room temperature, 300 and 600 °C. Structural thermal expansion coefficients show positive, linear expansion of a, b, c lattice constants and cell volume. In general, slightly higher expansion occurs along a and c directions. However, anisotropy decreases sharply with decreasing Fe content. Reversibility of thermal expansion in the investigated temperature range was checked by high-temperature diffraction studies under heating-up and cooling-down conditions. Impurities do not play an important role in thermal expansion of columbites; expansion coefficients measured on two crystals of the same sample characterized by different Ti content are in fact almost identical. Structural changes with temperature essentially affect bond lengths: volumes of both A and B octahedral sites increase linearly with temperature, whereas interpolyhedral geometrical parameters do not vary significantly.     

Infrared and Raman spectroscopy studies of the α–β phase transition in cristobalite

Infrared and Raman spectra of cristobalite are presented as a function of temperature through the phase transition. The modes are assigned and the assignments compared to those of earlier workers. The compatibility of modes at the G-point of the a-phase with the X and G-points of the ß-phase is given. In the transition region of ca. 500–550 K, smooth changes in intensity, frequency and linewidths are seen in many modes, indicative of coexistence of a- and ß-forms.     

Thermoelastic properties of minerals

The simple theory of equation of state recently developed by Kumar is used to investigate the temperature and pressure dependence of elastic moduli of MgO. The results are found to present good agreement with the experimental data. It is concluded that the Kumar formulation is far better than the Suzuki theory of thermal expansivity, and the Shanker formulation is not a new relation.     

Application of matrix analysis in delineating sinkhole risk areas along highway (I-70 near Frederick,Maryland)

Sinkhole collapse in the area of Maryland Interstate 70 (I-70) and nearby roadways south of Frederick, Maryland, has been posing a threat to the safety of the highway operation as well as other structures. The occurrence of sinkholes is associated with intensive land development. However, the geological conditions that have been developing over the past 200 million years in the Frederick Valley control the locations of the sinkholes. Within an area of approximately 8 km², 138 sinkholes are recorded and their spatial distribution is irregular, but clustered. The clustering indicates the existence of an interaction between the sinkholes. The point pattern of sinkholes is considered to be a sample of a Gibbsian point process from which the hard-core Strauss Model is developed. The radius of influence is calculated for the recorded sinkholes which are most likely to occur within 30 m of an existing sinkhole. The stochastic analysis of the existing sinkholes is biased toward the areas with intensive land use. This bias is adjusted by considering (1) topography, (2) proximity to topographic depressions, (3) interpreted rock formation, (4) soil type, (5) geophysical anomalies, (6) proximity to geologic structures, and (7) thickness of overburden. Based on the properties of each factor, a scoring system is developed and the average relative risk score for individual 30-m segments of the study area is calculated. The areas designated by higher risk levels would have greater risk of a sinkhole collapse than the areas designated by lower risk levels. This risk assessment approach can be updated as more information becomes available.     

Potential pollution of groundwater in the valley of the Seybouse River,north-eastern Algeria

In north-eastern Algeria, the Seybouse River is an important source of water used mainly for irrigation of large agricultural areas extending from the Guelma region to Annaba city. Industrial activities in this region contribute substantial water pollution to the river and the groundwater. Based on the different sources of pollution, mapping of areas vulnerable to groundwater pollution has been accomplished by combining land use and data on groundwater levels. The resulting maps show that the most vulnerable areas are those with large industrial activities—in Meboudja, Bouchegouf and Guelma. Infiltration and runoff contribute to pollution, and the highest infiltration rate is generally observed in areas of agricultural and industrial activities. Pollution of the aquifers in this area is of concern. Mountains, such as the Edough and Gelaat Bou Sbaa, contribute high runoff that carries pollutants towards the groundwater.     

Statistical models for the assessment of nitrate contamination in urban groundwater using GIS

The purpose of this study is to develop statistical models for groundwater quality assessment in urban areas using Geographic Information Systems (GIS). To develop the models, the concentrations of nitrate (expressed as nitrogen, NO₃-N), which are different according to the type of land use, well depth and distribution of rainfall, were analyzed in the Seoul (the capital of South Korea) area. Data such as land use, location of wells and groundwater quality data for nitrate contamination were collected and a database constructed within GIS. The distribution of NO₃-N concentrations is not normal, and the results of the Mann-Whitney U-test analysis show the difference of NO₃-N concentration by well depth and by distribution of rainfall. In both the shallow and deep wells, the radius of influence is 200 m in the dry season and 250 m in the rainy season, showing the tendency to increase in the rainy season. The results of correlation and regression analysis indicate that mixed residential and business areas and cropped field areas are likely to be the major contributor of increasing NO₃-N concentration. Land uses are better correlated with NO₃-N in deep wells than in shallow wells.