1: Subduction, slab detachment and mineralization: The Neogene in the Apuseni Mountains and Carpathians

The Inner Carpathians comprise several distinct Neogene late-stage orogenic Pb–Zn–Cu–Ag–Au ore districts. The mineral deposits in these districts are closely related to volcanic and subvolcanic rocks, and represent mainly porphyry and epithermal vein deposits, which formed within short periods of time in each district. Here, we discuss possible geodynamic and structural controls that suggest why some of the Neogene volcanic districts within the Carpathians comprise abundant mineralization, while others are barren. The Neogene period has been characterized by an overall geodynamic regime of subduction, where primary roll-back of the subducted slab and secondary phenomena, like slab break-off and the development of slab windows, could have contributed to the evolution, location and type of volcanic activity. Structural features developing in the overlying lithosphere and visible in the Carpathian crust, such as transtensional wrench corridors, block rotation and relay structures due to extrusion tectonics, have probably acted in focusing hydrothermal activity. As a result of particular events in the geodynamic evolution and the development of specific structural features, mineralization formed during fluid channelling within transtensional wrench settings and during periods of extension related to block rotation.In the Slovakian ore district of the Western Carpathians, Neogene volcanism and associated mineralization were localized by sinistral, NE-trending wrench corridors, which formed part of the extruding Alcapa block. The Baia Mare ore district, in the Eastern Carpathians, reflects a transtensional wrench setting on distributed oversteps close to the termination of the Dragos Voda fault. There, mineralization was spatially controlled by the transtensional Dragos Voda master fault and associated cross-fault systems. The Golden Quadrangle Cu–Au ore district of the Southern Apuseni Mountains reflects an unusual rotated transtensional/extensional setting close to the termination of a graben system. There, fluid flow was probably localized by fault propagation at the inner tip of the graben system.The spatial and temporal evolution of the magmatism and its changing geochemical signature from (N)W to (S)E strongly suggests a link with the contemporaneous northeastward roll-back of the subducted slab and a progressive southeastward detachment during accelerating roll-back. This geodynamic evolution is further supported by the present-day overall and detailed mantle lithospheric density images, the present-day heat flow patterns, the crustal architecture and its interpreted evolution, and the spatial and temporal evolution of depocentres around the Carpathian arc. In contrast to all these features, the mineral deposits in the West Carpathians, East Carpathians and Apuseni Mountains are too synchronous with respect to their individual volcanic history and contrast too much with younger volcanics of similar style, but barren, in southeastern parts of the Carpathians to simply link them directly to the slab evolution. In all three districts, the presence of magmatic fluids released from shallow plutons and their mixing with meteoric water were critical for mineralization, requiring transtensional or extensional local regimes at the time of mineralization, possibly following initial compressional regimes.These three systems show that mineralization was probably controlled by the superposition of favourable mantle lithospheric conditions and partly independent, evolving upper crustal deformation conditions.In the 13 to 11 Ma period the dominant mineralization formed all across the Carpathians, and was superimposed on structurally favourable crustal areas with, at that time, volcanic–hydrothermal activity. The period may reflect the moment when the (upper part of the) crust failed under lithospheric extension imposed by the slab evolution. This crustal failure would have fragmented the overriding plate, possibly breaking up the thermal lid, to provoke intensive fluid flow in specific areas, and allowed subsequent accelerated tectonic development, block rotation and extrusion of a “family of sub-blocks” that are arbitrarily regarded as the Tisia–Dacia or Alcapa blocks, even though they have lost their internal entity.     

Development of modified flyash as a permeable reactive barrier medium for a former manufactured gas plant site, Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (<1 μm) cubic highly crystalline precipitates on the flyash, although this new crystalline zeolite growth did not occur rapidly enough to enable productive zeolite formation. Surface area measurements showed that biofilm growth on the medium could be a major factor in the comparative reduction of surface area between real and synthetic contaminant groundwaters. The modified flyash was found to be a highly sorptive granular material that did not inhibit microbiological activity, however, leaching tests revealed that the medium would fail as a long-term barrier material.     

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits,Central Rhodopes,Bulgaria

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6–1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe³⁺. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300–200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.     

Trace element diffusion and incorporation in quartz during heating experiments

Heating of quartz crystals in order to study melt and high-temperature fluid inclusions is a common practice to constrain major physical and chemical parameters of magmatic and hydrothermal processes. Diffusion and modification of trace element content in quartz and its hosted melt inclusions have been investigated through step-heating experiments of both matrix-free quartz crystals and quartz crystals associated with sulfides and other minerals using a Linkam TS1500 stage. Magmatic and hydrothermal quartz were successively analyzed after each heating step for Cu, Al, and Ti using electron probe micro-analyzer. After the last heating step, quartz crystals and their hosted melt inclusions were analyzed by laser ablation inductively coupled plasma mass spectrometry and compared to unheated samples. Heated samples reveal modification of Cu, Li, Na, and B contents in quartz and modification of Cu, Li, Ag, and K concentrations in melt inclusions. Our results show that different mechanisms of Cu, Li, and Na incorporation occur in magmatic and hydrothermal quartz. Heated magmatic quartz records only small, up to a few ppm, enrichment in Cu and Na, mostly substituting for Li. By contrast, heated hydrothermal quartz shows enrichment up to several hundreds of ppm in Cu, Li, and Na, which substitute for originally present H. This study reveals that the composition of both quartz and its hosted melt inclusions may be significantly modified upon heating experiments, leading to erroneous quantification of elemental concentrations. In addition, each quartz crystal also becomes significantly enriched in Cu in the sub-surface layer during heating. We propose that sub-surface Cu enrichment is a direct indication of Cu diffusion in quartz externally sourced from both the surrounding sulfides as well as the copper pins belonging to the heating device. Our study shows that the chemical compositions of both heated quartz and its hosted inclusions must be interpreted with great caution to avoid misleading geological interpretations.