Mineral formation in an acid pit lake from a high-sulfidation ore deposit: Kirki, NE Greece

Open pit mining of base-metals from the high-sulfidation epithermal type deposit of Kirki (Thrace, NE Greece) resulted in the formation of an acid pit lake by infilling of the open cast by rain and draining waters after mine closure. The high toxic metals content of the ore, the limited buffering capacity of host rocks and the direct exposure of the ore zone to weathering result in an intense release of metals into the pit lake. The acidic and oxidative pit lake waters show high concentrations of trace metals. A mineral precipitate, covering the floor of the pit lake, comprises secondary anglesite, several species of the jarosite-group, rozenite, melanterite, wroewolfeite, gypsum, bukovskyite, beaverite, scorodite and minor goethite. The mineral precipitate presents a significant heavy metal content indicating effective removal of metals from the acid waters. Compared to other pit lakes in high-sulfidation type deposits it has a higher metal load, consistent with the mineralogy and grade of ore in pit walls.     

Three-dimensional hydrogeological modeling to assess the elevated-water-table technique for controlling acid generation from an abandoned tailings site in Quebec,Canada

The Manitou Mine sulphidic-tailings storage facility No. 2, near Val D’Or, Canada, was reclaimed in 2009 by elevating the water table and applying a monolayer cover made of tailings from nearby Goldex Mine. Previous studies showed that production of acid mine drainage can be controlled by lowering the oxygen flux through Manitou tailings with a water table maintained at the interface between the cover and reactive tailings. Simulations of different scenarios were performed using numerical hydrogeological modeling to evaluate the capacity of the reclamation works to maintain the phreatic surface at this interface. A large-scale numerical model was constructed and calibrated using 3 years of field measurements. This model reproduced the field measurements, including the existence of a western zone on the site where the phreatic level targeted is not always met during the summer. A sensitivity analysis was performed to assess the response of the model to varying saturated hydraulic conductivities, porosities, and grain-size distributions. Higher variations of the hydraulic heads, with respect to the calibrated scenario results, were observed when simulating a looser or coarser cover material. Long-term responses were simulated using: the normal climatic data, data for a normal climate with a 2-month dry spell, and a simplified climate-change case. Environmental quality targets were reached less frequently during summer for the dry spell simulation as well as for the simplified climate-change scenario. This study illustrates how numerical simulations can be used as a key tool to assess the eventual performance of various mine-site reclamation scenarios.

     

Origin of Low-K Intermediate Lavas at Nekoma Volcano, NE Honshu Arc, Japan: Geochemical Constraints for Lower-Crustal Melts

Extremely low-K basaltic andesite to andesite lavas at Nekomavolcano, situated in the frontal volcanic zone of the NE Honshuarc, were produced from melts that originated in the lower crust.Multiple incompatible trace element model calculations suggestthat extremely low-K basalt found in the same arc is a naturalanalog for the source composition. However, fractional crystallization,magma mixing, and crustal contamination models of primary low-Kbasalt cannot reproduce the Nekoma chemical composition. Derivationof melts from an extremely low-K amphibolitic lower-crustalrock with the residual mineral phases hornblende, olivine, pyroxenes,plagioclase, and magnetite is plausible. Major element compositionsof Nekoma lavas are very similar to those of experimental meltsof amphibolite dehydration melting, which further support theproposal. Light rare earth elements are slightly enriched, buttotal rare earth element abundances are relatively low, suggestinga high degree of partial melting of the source. Ba/Th ratiosare low for frontal arc lavas, reflecting modification of theratio during partial melting. Zr/Hf and Nb/Ta ratios are significantlygreater than is usual for arc lavas, suggesting an anomaloussource composition. Markedly low K, Rb, Cs contents in the extremelylow-K lavas are attributed to an extremely low-K source. Underplatingof an extremely low-K basalt originating from a hydrous depletedmantle wedge could form such an amphibolite. In contrast, Ndand Sr isotope ratios fall close to Bulk Earth values, indicatingan isotopically enriched source. Hornblende-bearing rocks maypredominate in the lower crust of the NE Honshu arc, based onthe observation of crustal xenoliths. The presence of largelow-V_p regions at lower-crustal depths beneath the frontal arcis suggested by geophysical observations. These observationsfurther support lower-crustal melting beneath Nekoma as theorigin of the intermediate low-K lavas. KEY WORDS: amphibolite source; crustal melting; low-K andesite; Sr–Nd isotopes; trace element     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Geochemical and Sr-Nd isotopic evidence for origin and evolution of the Miocene Pangeon granitoids,Southern Rhodope,Greece

The Sr-Nd isotopic ratios of selected post-collisional, calc-alkaline, I-type granitoids from the Pangeon pluton, intruding the lower tectonic unit (LTU) in the Southern Rhodope in the Miocene, support the existence of two types of granitoids (PTG porphyritic tonalite granodiorite and MGG biotite granodiorite to two-mica granite) unrelated by crystal fractionation and likely derived by partial melting of the same source under different P-T conditions. The Sr-Nd isotopic ratios of mafic enclaves in the granitoids as well as metamorphic rocks from the LTU have also been determined. At 22 Ma, the IR_Sr range between 0.706850 and 0.708381, whereas the ε_Nd(22) range from –3.86 to –1.05, with no relationship to granitoid types. The relationships between Sr and Nd isotopes as well as these isotopes and SiO₂ provide evidence of contamination of mafic melts by interaction with crust during magma differentiation. Both partial melting and AFC processes (r = 0.2) may account for compositional variations in the Pangeon magmas. The mafic enclaves display IR_Sr from 0.706189 to 0.707139, and ε_Nd(22) from –2.29 to –1.94, similar to the granitoids, supporting the hypothesis of a common origin. Amphibolites inferred to be subduction-enriched metabasalts under-plated crust during old subduction can represent the source of the Pangeon melts. The T_DM of the Pangeon granitoids is in the range 0.7–1.1 Ga for the inferred extraction age of the LILE-enriched subcontinental lithospheric mantle source. The upper crustal geochemical signatures and the relatively small isotopic composition of the Pangeon granitoids make these rocks similar to the coeval eastern-Mediterranean lamproites emplaced within the same geodynamic setting; this prompts similar melt sources. Lastly, the Pangeon granitoids display geochemical characteristics, isotopic ratios, and T_DM also similar to other Tertiary magmatic rocks from the Southern Rhodope and Biga peninsula, western Anatolia, suggesting a similar tectonic environment and co-magmatic evolution throughout the area.     

Geochemical evidence for arc-type volcanism in the Aegean Sea: the blueschist unit of Siphnos, Cyclades (Greece)

Blueschists, eclogites, chlorite–actinolite rocks and jadeite-gneisses of the blueschist unit of Siphnos have been investigated for their geochemical composition. Their protolith nature is characterised and a geodynamic model for the pre-metamorphic evolution of these metavolcanic rocks is proposed on the basis of immobile elements, especially trace elements and rare earth elements (REE).

The protoliths of the eclogites are characterised as calc-alkaline basalts, andesites and Fe-rich tholeiites evolving in an island-arc setting. Trace element data indicate that subducted marine sediments were assimilated in the magma chamber, enriching the protoliths in LILE and Pb. Produced in the early stage of back-arc basin opening, a protolith with affinities to both island-arc and MORB formed the precursor of the chlorite–actinolite rocks. They were created by low degrees of partial melting of very primitive magmas, akin to spinel-peridotites and have affinities to boninites, probably through melting of the peridotitic mantle wedge. Tholeiitic basalts and andesites with N-MORB affinity, especially in their REE-patterns, were then produced by partial melting, possibly in an embryonic back-arc basin. These rocks were the protoliths of the blueschists of Siphnos. Their enrichment in some LILE and Pb indicates a N-MORB source contaminated by marine sediments, probably shales or other Pb-rich sediments. Because the jadeite-gneisses show affinities to MOR-granites and volcanic arc granites, intrusion of their protoliths in a back-arc environment is likely. The protoliths of the quartz-jadeite gneisses are rhyodacites/dacites and rhyolites, those of the glaucophane-jadeite gneisses were andesites.

The proposed geodynamic model, solely based on geochemical data, is consistent with geochemical data from neighbouring islands, though those rock units show much higher chemical variability. Consistent with geotectonic models, which are based on structural and geophysical data, the volcanic protoliths of the Siphnos blueschist unit reflect the transition from subduction to spreading environment and record in detail: subduction, formation of an island-arc, and the evolution of a back-arc basin.     

Geochemical associations for evaluating the availability of potentially harmful elements in urban soils: Lessons learnt from Athens,Greece

The estimation of potentially harmful element (PHE) availability in urban soil is essential for evaluating impending risks for human and ecosystem health. In the present study five single extraction procedures were evaluated based on the analysis of 45 urban top-soil samples from Athens, Greece. The pseudototal (aqua regia), potentially phytoavailable (0.05 M EDTA), mobilizable (0.43 M HAc), bioaccessible (0.4 M glycine) and reactive pools (0.43 M HNO₃) of PHEs were determined. In general, geogenic elements in Athens soil (Ni, Cr, Co, As) are relatively less available than typical tracers of anthropogenic contamination (Pb, Zn, Cu, Cd). Results of principal component analysis (PCA) indicate an association between available fractions of Pb, Cu, Zn, Cd and amorphous Fe oxides, whereas amorphous Mn oxides account for the available concentrations of Mn, Ni and Co. Empirical multiple linear regression models demonstrate that pseudototal concentration is the predominant explanatory factor of variability for the available pools of the anthropogenic elements. Major elemental composition and total organic carbon (TOC) improve the predictions for the geogenic group of elements, although the explained variability remains low. Dilute HNO₃ is a better predictor of Zn, Ni, As and Mn availability, whereas Pb and Cu available fractions are predicted more accurately by the classical aqua regia protocol. This study contributes to the international database on the environmental behavior of PHEs and provides additional knowledge that can be used toward the harmonization of chemical extraction methodology in urban soil.     

Polybaric Geochemical Evolution of Two Shield Volcanoes from Santorini, Aegean Sea, Greece: Evidence for Zoned Magma Chambers from Cyclic Compositional Variations

Petrographic, mineralogic, and geochemical data are reportedfor lavas from two of the major shield volcanoes of the Santorinivolcanic complex (Skaros and Micro Profitis Ilias), both ofwhich were active prior to the well-known Minoan eruption withassociated caldera collapse. Field work and whole-rock chemicalanalyses indicate four cycles of eruptive activity within theSkaros sequence and three within the Micro Profitis Ilias (MP1) sequence. SiO₂ and LIL-element contents decrease from thebase to the top of all cycles except for the uppermost cycleof Skaros. Chemical variations within cycles are interpretedto result from eruption from compositionally and thermally zonedmagma chambers. Major oxide data and the results of least-squares, mass balancemodeling indicate that fractional crystallization played animportant role in the development of the observed chemical variations.However, observed systematic variations in groundmass compositionswithin each cycle, observed irregular variations in total phenocrystcontent and the results of density calculations require thatgeneration of the chemical zonation did not involve crystalsettling but reflects unstable density stratification, probablyresulting from sidewall crystallization. Some of the primitivelavas erupted on Santorini preserve phenocryst and xenocrystevidence for a stage of high-pressure fractional crystallization(involving removal of olivine, clinopyroxene, orthopyroxene,and Cr-spinel). Trace element data combined with petrographic data (i.e. theoccurrence of abundant phenocrysts with resorption textures)is taken as evidence that magma mixing was also important inthe development of cyclic variations. Most basaltic andesitesfrom Skaros appear to be hybrids derived by mixing of basaltand andesite/dacite. Mineralogic data demonstrate that mixingwas also important in the development of zonation in the chambersbeneath MPI, but trace element data cannot be explained by combinedfractionation and mixing alone. Specifically, incompatible,and compatible element abundances are lower than predicted iffractionation and mixing occurred and it is suggested that theanomalous trace element behaviour of especially LIL elementsreflects the simultaneous operation of assimilation, for whichthere is support from isotopic studies. It is concluded thatinter- cyclic chemical variations are explicable in terms offractionation, mixing and assimilation. The LIL element andhighly compatible element concentrations in the most primitivelavas erupted in each cycle of Skaros and MPI increase withtime, indicating that mixing became more important with time.     

Geochemical Evolution of Akagi Volcano, NE Japan: Implications for Interaction Between Island-arc Magma and Lower Crust, and Generation of Isotopically Various Magmas

Major and trace element, and Sr, Nd and Pb isotopic compositionswere determined for whole-rock samples from the ‘isotopicallyanomalous’ Akagi volcano in the volcanic front of theNE Japan arc. Sr and Nd isotopic compositions of phenocrystswere also analyzed together with their major and trace elementcompositions. Compared with the other volcanoes from the volcanicfront, the whole-rock isotope compositions of Akagi show highlyenriched characteristics; ⁸⁷Sr/⁸⁶Sr = 0·7060–0·7088,     

辽东南长海地区花岗质片麻岩类的地球化学特征:对其原岩性质及形成环境的制约

本文对辽东南长海地区花岗质片麻岩进行了系统的岩石学和地球化学研究,以便对其原岩性质及形成的构造环境给予制约。研究结果表明,研究区内花岗质片麻岩类可划分为富钠和富钾两类花岗质岩石,前者包括黑云二长花岗质片麻岩和花岗闪长质片麻岩,矿物组成主要包括斜长石、石英、黑云母及少量的钾长石等,后者则主要包括花岗质、二长花岗质和糜棱岩化花岗质片麻岩,其矿物组成以钾长石、斜长石、石英和次要的白云母和黑云母为主。地球化学分析结果显示,富钠花岗质片麻岩具有富硅、富钠、高铝、富集LREEs和LILEs、强烈亏损HREEs和HFSEs(Nb、Ta、P、Ti)、轻重稀土强烈分馏、并显示弱负Eu异常和Ba的相对亏损等特征;而富钾花岗质片麻岩则显示高硅、富钾、过铝质的地球化学属性、富集LREEs和LILEs、亏损HREEs和HFSEs,与富钠花岗质岩石相比,轻重稀土分馏程度相对较弱、HFSEs以及Ba相对于Rb和Th的亏损程度更强,并显示中等负Eu异常和强烈的Sr负异常等特征。上述特征表明,辽东南长海地区富钠花岗质片麻岩应起源于中酸性陆壳物质的部分熔融,并可能有玄武质物质的加入,原岩应为具有活动大陆边缘属性的花岗闪长岩,其形成应与狼林地块(或胶辽地块)东南及南部先存洋盆向陆块之下的俯冲作用相联系;而富钾花岗质片麻岩应形成于中酸性陆壳物质的部分熔融,原岩为具有碰撞型花岗岩属性的碱性花岗岩,其形成应与洋壳消减闭合、陆陆碰撞拼贴相联系。     

Geochemical and Sr–Nd isotopic evidence for the genesis of the Late Cainozoic Almopia volcanic rocks (Central Macedonia, Greece)

Summary ?Major and trace element contents and Sr–Nd isotope ratios of selected volcanics of Pliocene age from the Almopia area, central Macedonia, Greece, have been determined. These rocks are mainly distinguished as two groups based on geographical, petrological and isotopic data: a) the east–central western group (E–CW) and b) the south western group (SW). The absence of contemporaneous basic volcanics in the Almopia area coupled with the considerable scatter of elements in variation diagrams rule out fractional crystallization as the dominant differentiation process. Instead, disequilibrium textures along with the positive correlation of Sr-isotope ratios with differentiation suggest mixing between a basic and an acid component combined with assimilation and fractionation. The spider diagrams of the most silica-poor volcanics show evidence of subduction-related processes, indicating that the parental magmas may have been derived from partial melting of mantle wedge enriched in LILE and LREE by subducted slab-derived fluids. Previous data on the oxygen isotope composition of the same volcanics are consistent with this genetic hypothesis. Lastly, the relatively high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd ratios (0.7080 and 0.512370, respectively) of the volcanic sample inferred to be compositionally the closest one to the parental magma of Almopia rocks suggest that the incompatible element enrichment of the mantle source is old, probably of Proterozoic age. Received December 12, 2001; revised version accepted June 20, 2002 Published online November 29, 2002     

Petrography and geochemistry of the late Eocene–early Oligocene submarine fans and shelf deposits on Lemnos Island,NE Greece. Implications for provenance and tectonic setting

Provenance and tectonic history of the late Eocene‐early Oligocene submarine fans and shelf deposits on Lemnos Island, NE Greece, were studied using sandstone framework composition, sedimentological data and sandstone and mudstone geochemistry. The resulting tectonic–sedimentological model is based on the late Eocene–early Oligocene Lemnos Island being in a forearc basin with the outer arc ridge as a major sediment source. Modal petrographic analysis of the studied sandstones shows that the source area comprises sedimentary, metamorphic and plutonic igneous rocks deposited in the studied area in a recycled orogenic environment. Moreover, within the above sediments, the minor occurrence of volcanic fragments suggests little or no influence of a volcanic source. Provenance results, based on major, trace and rare earth element (REE) data, suggest an active continental margin/continental island arc signature. All the samples are LREE, enriched relative to HREE, with a flat HREE pattern and positive Eu anomalies, suggesting that the processes of intracrustal differentiation (involving plagioclase fractionation) were not of great importance. Results derived from the multi‐element diagrams also suggest an active margin character, and a mafic/ultramafic source rock composition, while the positive anomaly of Zr that can be attributed to a passive continental margin source, is most likely associated with reworking and sorting during sediment transfer. Palaeocurrents, with a NE–NNE direction, indicate a northeast flow, towards the location of the late Eocene–early Oligocene magmatic belt in the north‐east Aegean region. Conglomerates are composed of chert, gneiss and igneous fragments, such as basalts and gabbros, suggesting this outer arc ridge as a likely source area. Copyright © 2009 John Wiley & Sons, Ltd.