Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

Extensional Late Paleozoic deformation on the western margin of Pangea, Patlanoaya area, Acatlán Complex, southern Mexico

New mapping in the northern part of the Paleozoic Acatlán Complex (Patlanoaya area) records several ductile shear zones and brittle faults with normal kinematics (previously thought to be thrusts). These movement zones separate a variety of units that pass structurally upwards from: (i) blueschist-eclogitic metamorphic rocks (Piaxtla Suite) and mylonitic megacrystic granites (Columpio del Diablo granite ≡ Ordovician granites elsewhere in the complex); (ii) a gently E-dipping, listric, normal shear zone with top to the east kinematic indicators that formed under upper greenschist to lower amphibolite conditions; (iii) the Middle–Late Ordovician Las Minas quartzite (upper greenschist facies psammites with minor interbedded pelites intruded by mafic dikes and a leucogranite dike from the Columpio del Diablo granite) unconformably overlain by the Otate meta-arenite (lower greenschist facies psammites and pelites): roughly temporal equivalents are the Middle–Late Ordovician Mal Paso and Ojo de Agua units (interbedded metasandstone and slate, and metapelite and mafic minor intrusions, respectively) — some of these units are intruded by the massive, 461 ± 2 Ma, Palo Liso megacrystic granite: decussate, contact metamorphic muscovite yielded a ⁴⁰Ar/³⁹Ar plateau age of 440 ± 4 Ma; (iv) a steeply-moderately, E-dipping normal fault; (v) latest Devonian–Middle Permian sedimentary rocks (Patlanoaya Group: here elevated from formation status). The upward decrease in metamorphic grade is paralleled by a decrease in the number of penetrative fabrics, which varies from (i) three in the Piaxtla Suite, through (ii) two in the Las Minas unit (E-trending sheath folds deformed by NE-trending, subhorizontal folds with top to the southeast asymmetry, both associated with a solution cleavage), (iii) one in the Otate, Mal Paso, and Ojo de Agua units (steeply SE-dipping, NE–SW plunging, open-close folds), to (iv) none in the Patlanoaya Group. ⁴⁰Ar/³⁹Ar analyses of muscovite from the earliest cleavage in the Las Minas unit yielded a plateau age of 347 ± 3 Ma and show low temperature ages of  260 Ma. Post-dating all of these structures and the Patlanoaya Group are NE-plunging, subvertical folds and kink bands. An E–W, vertical normal fault juxtaposes the low-grade rocks against the Anacahuite amphibolite that is cut by megacrystic granite sheets, both of which were deformed by two penetrative fabrics. Amphibole from this unit has yielded a ⁴⁰Ar/³⁹Ar plateau age of 299 ± 6 Ma, which records cooling through  490 °C and is probably related to a Permo-Carboniferous reheating event during exhumation. The extensional deformation is inferred to have started in the latest Devonian ( 360 Ma) during deposition of the basal Patlanoaya Group, lasting through the rapid exhumation of the Piaxtla Suite at  350–340 Ma synchronous with cleavage development in the Las Minas unit, deposition of the Patlanoaya Group with active fault-related exhumation suggested by Mississippian and Early Permian conglomerates ( 340 and 300 Ma, respectively), and continuing at least into the Middle Permian (≡ 260 Ma muscovite ages). The continuity of Mid-Continent Mississippian fauna from the USA to southern Mexico suggests that this extensional deformation occurred on the western margin of Pangea after closure of the Rheic Ocean.     

Numerical modeling for analyzing thermal surface anomalies induced by underground coal fires

Coal seams burning underneath the surface are recognized all over the world and have drawn increasing public attention in the past years. Frequently, such fires are analyzed by detecting anomalies like increased exhaust gas concentrations and soil temperatures at the surface. A proper analysis presumes the understanding of involved processes, which determine the spatial distribution and dynamic behavior of the anomalies.In this paper, we explain the relevance of mechanical and energy transport processes with respect to the occurrence of temperature anomalies at the surface. Two approaches are presented, aiming to obtain insight into the underground coal fire situation: In-situ temperature mapping and numerical simulation. In 2000 to 2005, annual temperature mapping in the Wuda (Inner Mongolia, PR China) coal fire area showed that most thermal anomalies on the surface are closely related to fractures, where hot exhaust gases from the coal fire are released. Those fractures develop due to rock mechanical failure after volume reduction in the seams. The measured signals at the surface are therefore strongly affected by mechanical processes.More insight into causes and effects of involved energy transport processes is obtained by numerical simulation of the dynamic behavior of coal fires. Simulations show the inter-relation between release and transport of thermal energy in and around underground coal fires. Our simulation results show a time delay between the coal fire propagation and the observed appearance of the surface temperature signal. Additionally, the overall energy flux away from the burning coal seam into the surrounding bedrock is about 30-times higher than the flux through the surface. This is of particular importance for an estimation of the energy released based on surface temperature measurements. Finally, the simulation results also prove that a fire propagation rate estimated from the interpretation of surface anomalies can differ from the actual rate in the seam.     

Mineralogy and composition of Kuroko deposits from northeastern Honshu and their possible modern analogues from the Izu-Ogasawara (Bonin) Arc south of Japan: Implications for mode of formation

The Kuroko deposits of NE Honshu are a key type deposit for the study of volcanogenic massive sulfide deposits. However, these deposits have not been studied in detail since the early 1980's and knowledge of their mode of formation is now dated. In this study, we present the analysis of 12 samples of the Kuroko deposits, 12 samples of submarine hydrothermal minerals from the Sunrise deposit and 6 samples from Suiyo Seamount, both of which are located on the Izu-Ogasawara (Bonin) Arc, for 27 elements. For the Kuroko deposit, Cd>Sb>Ag>Pb>Hg>As>Zn>Cu are highly enriched, Au>Te>Bi>Ba>Mo are moderately enriched, In>Tl are somewhat enriched and Fe is not significantly enriched relative to the average continental crust. Within each of these deposits, a similar pattern of element associations is apparent: Zn–Pb with As, Sb, Cd, Ag, Hg, Tl and Au; Fe–Cu–Ba with As, Sb, Ag, Tl, Mo, Te and Au; Si–Ba with Ag and Au; CaSO₄. The enrichment of the chalcophilic elements in these deposits is consistent with hydrothermal leaching of these elements from the host rocks which are dominantly rhyolite–dacite in the case of the Kuroko deposits, rhyolite in the case of the Sunrise deposit and dacite–rhyolite in the case of the Suiyo Seamount deposit. However, this pattern of element enrichment is also similar to that observed in fumarolic gas condensates from andesitic volcanoes. This suggests that there may be a significant magmatic contribution to the composition of the hydrothermal fluids responsible for the formation of the Kuroko deposits, although it is not yet possible to quantify the relative contributions of these two sources of elements.The compositional data show that Sunrise and Suiyo Seamount deposits are much closer compositionally to the Kuroko deposits from NE Honshu than are the submarine hydrothermal deposits from the JADE site in the Okinawa Trough which contain, on average, significantly higher concentrations of Pb, Zn, Sb, As and Ag than each of these deposits. In spite of the greater similarity in tectonic setting of the Hokuroku Basin in which the Kuroko deposits formed to the Okinawa Trough (intracontinental rifted back-arc basin) compared to Myojin Knoll and Suiyo Seamount (active arc volcanoes), it appears that submarine hydrothermal deposits from Myojin Knoll and Suiyo Seamount are closer analogues of the Kuroko deposit than are those from the Okinawa Trough. The present data are consistent with the magmatic hydrothermal model for the formation of Kuroko-type deposits as formulated by Urabe and Marumo [Urabe, T., Marumo, K., 1991. A new model for Kuroko-type deposits of Japan. Episodes 14, 246–251].     

Mapping Proterozoic unconformity-related uranium deposits in the Rockhole area, Northern Territory, Australia using landsat ETM+

The Rockhole area, Northern Territory, Australia, hosts a number of Proterozoic unconformity-related uranium deposits. The geology of the area features within Paleoproterozoic rocks of the Pine Creek Orogen, near the unconformity with overlying platform cover sandstone of the Paleo- to Mesoproterozoic McArthur Basin. Landsat Enhanced Thematic Mapper plus (ETM+) data was used in the Rockhole area to assist in mapping geological structures and lithology, and to identify anomalous concentrations of ferrous minerals, the product of alteration, which can be indicators of buried uranium mineralization. Several image-processing procedures were applied to the ETM+ data to identify, isolate and enhance mineralogical information as simple and complex false color composites. ETM+ 754 shown as red green and blue respectively was the best simple image. Overall, complex images based on Principal Component Analysis proved to be the most useful products. Sandstone, shale and siltstone, the target lithologies, Koolpin Formation, the target stratigraphic unit, and bleaching pattern due to the removal of iron(II) compounds, the target alteration pattern, were confidently mapped to provide information required by the mineral emplacement model, which ultimately identified areas of likely uranium mineralization. Thus the contrasting behavior of the two principle oxidation states of uranium and iron can be utilized to map/delineate bleached alteration zones associated with economic concentrations of uranium using multispectral sensors like Landsat or better hyperspectral sensors.     

Ultrahigh pressure macro diamonds from Copeton (New South Wales, Australia), based on Raman spectroscopy of inclusions

Mining of Cenozoic alluvial deposits at Copeton and Bingara (Eastern Australia) has produced two million macrodiamonds (0.25 ct median size). Raman spectroscopy is used to identify included minerals within uncut Copeton diamonds, with sealed chamber remnant pressures of 31.7 to 35.6 kbar for coesite, 13.6 and 22.7 kbar for clinopyroxene, and 7.6 kbar for grossular garnet. Assuming elastic behaviour, these values generate inclusion entrapment PT loci which intersect, restricting diamond formation conditions: from 250 °C, 43 kbar to 800 °C, 52 kbar. Larger than error (± 100 °C and ± 4 kbar), this range shows a systematic variation in inclusion composition with diamond zoning and N properties. Published research shows 1) Copeton and Bingara diamonds are unique, and 2) modern alluvium in the Bingara district carries mantle-formed garnet, captured by post-tectonic alkali basalt from an extensive diamondiferous ultrahigh pressure (UHP) terrane that stalled at depth because it is dominated by mafic eclogite. The combined Raman and geological results indicate two sets of subduction UHP diamond formation conditions/protolith are required, firstly cooler oceanic slab and secondly including higher temperature continental crust. The Copeton and Bingara stones are UHP macrodiamonds, and Carboniferous ⁴⁰Ar/³⁹Ar age dates on clinopyroxene inclusions should be interpreted as ages of crystallisation, representing the termination of subduction. The characteristic features of ruptured inclusions and etched percussion marks on Copeton and Bingara diamond indicate volcanic delivery to the earth's surface. Alluvial deposits elsewhere in Eastern Australia may carry similar diamond along with diamond of different origin.     

Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ¹³C_org isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from 2.5% to 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of P_reactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The C_org/P_total and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.     

The role of heterogeneous strain in the development and preservation of a polymetamorphic record in high-P granulites, western Canadian Shield

Mafic rocks in the Chipman domain of the Athabasca granulite terrane, western Canadian Shield, provide the first well‐documented record of two distinct high‐P granulite facies events in the same domain in this region. Textural relations and the results of petrological modelling (NCFMASHT system) of mafic granulites are interpreted in terms of a three‐stage tectonometamorphic history. Stage 1 involved development of the assemblage Grt + Cpx + Qtz ± Pl (M₁) from a primary Opx‐bearing igneous precursor at conditions of 1.3 GPa, 850–900 °C. Field and microstructural observations suggest that M₁ developed synchronously with an early S₁ gneissic fabric. Stage 2 is characterized by heterogeneous deformation (D₂) and synkinematic partial retrogression of the peak assemblage to an amphibole‐bearing assemblage (M₂). Stage 3 involved a third phase of deformation and a return to granulite facies conditions marked by the prograde breakdown of amphibole (Amph₂) to produce matrix garnet (Grt_3a) and the coronitic assemblage Cpx_3b + Opx_3b + Ilm_3b + Pl_3b (M_3b) at 1.0 GPa, 800–900 °C. M₁ and M_3b are correlated with 2.55 and 1.9 Ga metamorphic generations of zircon, respectively, which were dated in a separate study. Heterogeneous strain played a crucial role in both the development and preservation of these rare examples of multiple granulite facies events within single samples. Without this fortuitous set of circumstances, the apparent reaction history could have incorrectly led to an interpretation involving a single‐cycle high‐grade event. The detailed P–T–t–D history constructed for these rocks provides the best evidence to date that much of the east Lake Athabasca region experienced long‐term lower crustal residence from 2.55 to 1.9 Ga, and thus the region represents a rare window into the reactivation and ultimate stabilization processes of cratonic lithosphere.     

The effect of extracellular polymers (EPS) on the proton adsorption characteristics of the thermophile Bacillus licheniformis S-86

This study investigated proton adsorption to an extracellular polymeric substance (EPS) producing bacterial strain, Bacillus licheniformis S-86, in order to characterise and quantify the contribution made by EPS to cell surface reactivity. Potentiometric titrations were conducted using both untreated cells and cells from which the EPS layer had been extracted. Surface-complexation modelling indicated the presence of four different functional groups in both untreated and EPS-free cells. These sites are assigned to phosphodiester, (pK_a 3.3–3.4), carboxylic (pK_a 5.3–5.4), phosphoryl/ (pK_a 7.4–7.5) and hydroxyl/amine (pK_a 9.9–10.1) type groups. The pK_a values for the four groups were very similar for untreated and EPS-free cells, indicating no qualitative difference in composition, but site concentrations in the untreated cells were statistically found to be significantly higher than those in the EPS-free cells for the pK_a 3.3–3.4 and pK_a 9.9–10.1 sites. Infrared analysis provided supporting evidence that site 2 is carboxylic in nature but did not reveal any difference in IR absorption between the native and EPS-free cells. Dissolved organic carbon (DOC) analysis conducted during this study indicated that DOC release by cells is significant, and that the EPS layer is the major contributor.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.