A geochemical model for removal of iron(II)(aq) from mine water discharges

A steady state geochemical model has been developed to assist in understanding surface-catalysed oxidation of aqueous Fe(II) by O₂(aq), which occurs rapidly at circumneutral pH. The model has been applied to assess the possible abiotic removal of Fe(II)(aq) from alkaline ferruginous mine water discharges using engineered reactors with high specific-surface area filter media. The model includes solution and surface speciation equilibrium, oxidation kinetics of dissolved and adsorbed Fe(II) species and mass transfer of O₂(g). Limited field data for such treatment of a mine water discharge were available for model development and assessment of possible parameter values. Model results indicate that an adsorption capacity between 10⁻⁶ and 10⁻⁵ mol l⁻¹ is sufficient for complete removal, by oxidation, of the Fe(II)(aq) load at the discharge. This capacity corresponds approximately to that afforded by surface precipitation of Fe(III) oxide onto plastic trickling filter media typically used for biological treatment of wastewater. Extrapolated literature values for microbial oxidation of Fe(II)(aq) by neutrophilic microbial populations to the simulated reactor conditions suggested that the microbially-mediated rate may be several orders-of-magnitude slower than the surface-catalysed oxidation. Application of the model across a range of mine water discharge qualities shows that high Fe(II)(aq) loadings can be removed if the discharge is sufficiently alkaline. Additional reactor simulations indicate that reactor efficiency decreases dramatically with pH in the near acid region, coinciding with the adsorption edge for Fe²⁺ on Fe oxyhydroxide. Alkaline discharges thus buffer pH within the range where Fe(II)(aq) adsorbs onto the accreting Fe hydroxide mineral surface, and undergoes rapid catalytic oxidation. The results suggest that the proposed treatment technology may be appropriate for highly ferruginous alkaline discharges, typically associated with abandoned deep coal mines.     

淡色花岗岩的岩石学和地球化学特征及其成因

淡色花岗岩(leucogranite)是一类高铝高硅碱的酸性侵入岩,主要地球化学特征是:SiO2≥72%,Al2O3≥14%,Na2O+K2O~8.5%,富Rb,亏损Th、Ba、Sr,稀土总量较一般花岗岩低(∑REE=(40~120)×10-6),且表现为中等分异的轻稀土弱富集型,一般具有Eu负异常;Sr-Nd-Pb-O同位素指示其岩浆明显的陆壳来源。淡色花岗岩主要发育于陆壳(俯冲)碰撞加厚带,由逆冲折返的俯冲板片变沉积岩部分经过脱水熔融产生。淡色花岗岩可划分为三种不同的岩石类型:(1)二云母型淡色花岗岩,由变泥质岩(或变硬砂岩)在中地壳水平经黑云母(和/或白云母)脱水熔融产生;(2)电气石型淡色花岗岩,由变泥质岩在较低温度下经白云母脱水熔融产生;(3)石榴子石型淡色花岗岩,由长英质下地壳经黑云母脱水熔融产生。源区残留独居石、磷灰石等富REE矿物是淡色花岗岩亏损REE、Th等元素的原因。源岩为变泥质岩及源区残留钾长石是淡色花岗岩亏损Sr、Ba的主要原因。     

Geodynamic significance of the Raspas Metamorphic Complex (SW Ecuador): geochemical and isotopic constraints

The Raspas Metamorphic Complex of southwestern Ecuador is regarded as the southernmost remnant of oceanic and continental terranes accreted in the latest Jurassic–Early Cretaceous. It consists of variably metamorphosed rock types. (1) Mafic and ultramafic rocks metamorphosed under high-pressure (HP) conditions (eclogite facies) show oceanic plateau affinities with flat REE chondrite-normalized patterns, Nd_{150 Ma} ranging from +4.6 to 9.8 and initial Pb isotopic ratios intermediate between MORB and OIB. (2) Sedimentary rocks metamorphosed under eclogitic conditions exhibit LREE enriched patterns, strong negative Eu anomalies, Rb, Nb, U, Th, Pb enrichments, low Nd_{150 Ma} values (from −6.4 to −9.5), and high initial ⁸⁷Sr/⁸⁶Sr and ^206,207,208Pb/²⁰⁴Pb isotopic ratios suggesting they were originally sediments derived from the erosion of an old continental crust. (3) Epidote-bearing amphibolites show N-MORB affinities with LREE depleted patterns, LILE, Zr, Hf and Th depletion, high Nd_{150 Ma} (>+10) and low initial Pb isotopic ratios.The present-day well defined internal structure of the Raspas Metamorphic Complex seems to be inconsistent with the formerly proposed interpretation of a “tectonic mélange”. The association of oceanic plateau rocks and continent-derived sediments both metamorphosed in HP conditions suggests that the thin edge of the oceanic plateau first entered the subduction zone and dragged sediments downward of the accretionary wedge along the Wadatti–Benioff zone. Subsequently, when its thickest part arrived into the subduction zone, the oceanic plateau jammed the subduction processes, due to its high buoyancy.In Ecuador and Colombia, the latest Jurassic–Early Cretaceous suture involves HP oceanic plateau rocks and N-MORB rocks metamorphosed under lower grades, suggesting a composite or polyphase nature for the latest Jurassic–Early Cretaceous accretionary event.     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

Geochronological and geochemical constraints on the Cuonadong leucogranite,eastern Himalaya

First comprehensive investigations of the Cuonadong leucogranite exposed in North Himalayan gneiss dome of southern Tibet are presented in this study. The SIMS U–Pb ages of oscillatory zircon rims scatter in a wide range from 34.1 to 16.0 Ma, and the Cuonadong leucogranite probably emplaced at 16.0 Ma. High-precision ⁴⁰Ar/³⁹Ar dating on a muscovite sample yields an essentially flat age spectrum with consistent plateau and isochron ages, indicating that the Cuonadong leucogranite cooled below 450 °C at 14 Ma. Based on the youngest zircon U–Pb age and muscovite ⁴⁰Ar/³⁹Ar age, the Cuonadong leucogranite experienced rapid cooling with a rate of 119 °C/Myr from 16 to 14 Ma. The geochronological data of this undeformed leucogranite also suggest that the ductile extension of the South Tibetan Detachment System in the eastern Himalaya ceased by ca. 14 Ma. Furthermore, the initial Sr–Nd isotopic compositions and Nd model ages demonstrate that the leucogranite was derived from metapelitic source within the Greater Himalayan Crystalline Complex. The distinct Ba depletion with high Rb/Sr ratios and negative Eu anomalies make it clear that the leucogranite melts were generated by breakdown of muscovite under fluid-absent conditions.     

Petrogenesis of the Sabongari alkaline complex,cameroon line (central Africa): Preliminary petrological and geochemical constraints

The petrography, mineral chemistry and geochemical features of the Sabongari alkaline complex are presented and discussed in this paper with the aim of constraining its petrogenesis and comparing it with other alkaline complexes of the Cameroon Line. The complex is mainly made up of felsic rocks: (i) granites predominate and include pyroxene–amphibole (the most abundant), amphibole–biotite, biotite and pyroxene types; (ii) syenites are subordinate and comprise amphibole–pyroxene and amphibole–biotite quartz syenites; (iii) pyroxene–amphibole–biotite trachyte and (iv) relatively abundant rhyolite. The minor basic and intermediate terms associated with felsic rocks consist of basanites, microdiorite and monzodioites. Two groups of pyroxene bearing rocks are distinguished: a basanite–trachyte–granite (Group 1) bimodal series (SiO₂ gap: 44 and 63 wt.%) and a basanite–microdiorite–monzodiorite–syenite–granite (Group 2) less pronounced bimodal series (reduced SiO₂ gap: 56–67 wt.%). Both are metaluminous to peralkaline whereas felsic rocks bare of pyroxene (Group 3) are metaluminous to peraluminous. The Group 1 basanite is SiO₂-undersaturated (modal analcite in the groundmass and 11.04 wt.% normative nepheline); its Ni (240 ppm) and Cr (450 ppm) contents, near mantle values, indicate its most primitive character. The Group 2 basanite is rather slightly SiO₂-saturated (1.56 wt.% normative hypersthene), a marker of its high crustal contamination (low Nb/Y-high Rb/Y). The La/Yb and Gd/Yb values of both basanites (1: 19.47 and 2.92; 2: 9.09 and 2.23) suggest their common parental magma composition, and their crystallization through two episodes of partial melting (2% and 3% respectively) of a lherzolite mantle source with <4% residual garnet. The effects of crustal contamination were selectively felt in the values of HFSE/LREE, LREE/LILE and LREE/HFSE ratios, known as indicators. Similar features have been recently obtained in the felsic lavas of the Cameroon Volcanic Line.     

Kinetics of iron (II) oxidation determined in the field

This paper presents the results of extensive field trials measuring rates of Fe(II) oxidation at a number of Fe-bearing mine drainage discharges in the UK. Batch experiments were carried out with samples taken at regular intervals and Fe(II) concentration determined spectrophotometrically using 2′2-bipyridyl as the complexing agent. Initial concentrations for Fe(II) were 5.65-76.5 mg/L. Temperature, pH and dissolved O₂ (DO) were logged every 10 s, with pH at the start of the experiments in the range 5.64-6.95 and alkalinity ranging from 73 to 741 mg/L CaCO₃ equivalent. A numerical model based on a fourth order Runge-Kutta method was developed to calculate values for k₁, the rate constant for homogeneous oxidation, from the experimental data. The measured values of pH, temperature, [Fe(II)] and DO were input into the model with resulting values for k₁ found to be in the range 2.7 × 10¹⁴-2.7 × 10¹⁶ M⁻² atm⁻¹ min⁻¹. These values for k₁ are 1-3 orders of magnitude higher than previously reported for laboratory studies at a similar pH. Comparison of the observed Fe(II) oxidation rates to data published by other authors show a good correlation with heterogenous oxidation rates and may indicate the importance of autocatalysis in these systems. These higher than expected rates of Fe oxidation could have a significant impact on the design of treatment schemes for the remediation of mine drainage and other Fe-bearing ground waters in the future.     

A geochemical traverse across the Eastern Carpathians (Romania): constraints on the origin and evolution of the mineral water and gas discharges

The inner sector of the Eastern Carpathians displays a large number of Na–HCO₃, CO₂-rich, meteoric-originated cold springs (soda springs) and bore wells, as well as dry mofettes. They border the southern part of the Pliocene–Quaternary Calimani–Gurghiu–Harghita (CGH) calc-alkaline volcanic chain. Both volcanic rocks and CO₂-rich emissions are situated between the eastern part of the Transylvanian Basin and the main east Carpathian Range, where active compression tectonics caused diapiric intrusions of Miocene halite deposits and associated saline, CO₂-rich waters along active faults. The regional patterns of the distribution of CO₂ in spring waters (as calculated pCO₂) and the distribution pattern of the ³He/⁴He ratio in the free gas phases (up to 4.5 R_m/R_a) show their maximum values in coincidence with both the maximum heat-flow measurements and the more recent volcanic edifices. Moving towards the eastern external foredeep areas, where oil fields and associated brines are present, natural gas emissions become CH₄-dominated. Such a change in the composition of gas emissions at surface is also recorded by the ³He/⁴He ratios that, in this area, assume ‘typical’ crustal values (R_m/R_a=0.02).In spite of the fact that thermal springs are rare in the Harghita volcanic area and that equilibrium temperature estimates based on geothermometric techniques on gas and liquid phases at surface do not suggest the presence of shallow active hydrothermal systems, a large circulation of fluids (gases) is likely triggered by the presence of mantle magmas stored inside the crust. If total ³He comes from the mantle or from the degassing of magmas stored in the crust, CO₂ might be associated to both volcanic degassing and thermometamorphism of recently subducted limestones.     

New chronological and geochemical constraints on the genesis and geological evolution of Ponza and Palmarola Volcanic Islands (Tyrrhenian Sea, Italy)

A new geochronological and geochemical study of the volcanic rocks of the Ponza and Palmarola Islands, Pontine Archipelago, has been carried out. This archipelago is located along the boundary between the Italian continental shelf and the opening Tyrrhenian basin. It is a key area to study volcanism related to the opening of the Tyrrhenian Sea. Ponza is the oldest felsic magmatic manifestation in the central Tyrrhenian area. Previous studies suggested that Ponza volcanic activity began before 5 Ma. Twenty-five new K–Ar ages constrain the volcanic activity (rhyolitic hyaloclastites and dykes) to the last 4.2 Ma, with two episodes of quiescence between 3.7 and 3.2 Ma and between 2.9 and 1.0 Ma. A new volcanic episode dated at 3.2–2.9 Ma has been identified on the central and southern Ponza, with emplacement of pyroclastic units. At 1.0 Ma, a trachytic episode ended the volcanic activity. The near island of Palmarola exhibits rhyolitic hyaloclastites and domes dated between 1.6 and 1.5 Ma, indicating that the island was entirely built during the Early Pleistocene in a short span of time of ca. 120 ka. Although only 6–8 km apart, the two islands display significantly different geochemical signatures. Ponza rhyolites show major and trace element compositions representative of orogenic magmas of subduction/collision zones: high-K calc-alkaline and metaluminous rhyolites (Agpaitic Index [AI] and Alumina Saturation Index [ASI] <1), high LILE/HFSE (Th/Ta=16–21) and LREE/HFSE ratios (La/Nb>3), and Nb–Ta negative anomalies. In Palmarola, the orogenic character is also present, but much less marked than in Ponza: rhyolites have a peralkaline character (AI>1), lower LILE/HFSE (Th/Ta=11–15), low LREE/HFSE ratios (La/Nb=1–2) close to those of anorogenic lavas, and the Nb–Ta negative anomalies are almost absent. Y/Nb ratios indicate different magmatic sources, one similar to island-arc or active continental margin basalts for Ponza rhyolites, and the others probably involving an OIB type component for Palmarola rhyolites and Ponza trachytes. Palmarola volcanics represent a transitional magmatism: although a preserved collisional geochemical imprint, they show geochemical features approaching those of anorogenic lavas erupted in a within-plate context. The change of magmatism evidenced in this study can be related to the tectonic evolution of the area. Indeed, Hf, Ta and Rb contents suggest that the oldest Pliocene rhyolites of Ponza would emplace in a syn- to late-collisional setting, while the younger Pleistocene rhyolites of Palmarola would be emplaced in a post-collisional setting in which the orogenic character (Th/Ta) decreases and mantle influence (Nb/Ta) increases. Geochemical modeling strongly suggests that the Palmarola rhyolites represent the waning stages of a subduction-related magmatism. The K–Ar datings allow us to estimate precisely the transition of magmatism to last less than 1.3 Ma. The transitional magmas may be the result of the upwelling of asthenospheric mantle inducing melting of a metasomatized lithospheric mantle and the mixing between these two sources. This upwelling could occur during the extension of the Tyrrhenian basin, caused by the slab retreat and steepening, or during a process of slab break-off starting in the Pliocene.     

Pb and Sr isotope and geochemical data from the Pb–Zn deposit Bleiberg (Austria): constraints on the age of mineralization

Summary The timing of Zn–Pb mineralization hosted by early dolomitized lagoonal limestones (Crest facies) at Bleiberg (Carinthia, Austria) has been constrained using Sr-isotopes. This late stage Zn–Pb mineralization is a special feature of the Bleiberg deposit. Samples of the mineralized Crest facies are characterized by higher concentrations of minor and trace elements (except Ba and Sr) compared to samples from the weakly mineralized Wetterstein limestone of the lagoonal facies. The samples from the Crest facies indicate that a fluid with a minimum ⁸⁷Sr/⁸⁶Sr ratio of 0.7083 reacted at 210±30 Ma with carbonate rocks having ⁸⁷Sr/⁸⁶Sr ratios of approximately 0.7077 during a late stage of ore formation. The ⁸⁷Sr/⁸⁶Sr ratios correlate with the Mn and Cl concentrations. Lead isotope data of whole rock samples of Bleiberg yielded an isochron age of 180±40 Ma. They furthermore confirm the presence of two types of common lead; an isotopically distinct ore lead component is present within and close to the ore bodies. The other common Pb component is present in host rocks and in gangue minerals and is distinguished from the ore lead by lower ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios. The Sr and the Pb ages are consistent with geological evidence indicating a Triassic age of Pb–Zn mineralization and support genetic models emphasizing the role of bacteriogenic sulfate reduction at low temperatures prior to subsidence and burial. Elevated ⁸⁷Sr/⁸⁶Sr values (>0.7080) of gangue minerals indicate an epigenetic origin of strontium. Our results are consistent with a genetic model postulating formation of the ore-bearing hydrothermal fluids “at depth” where they leached lead from pre-Upper Carboniferous basement rocks.     

Geochronological and geochemical constraints on the origin of the Southeast Anatolian ophiolites,Turkey

The Southeast Anatolian ophiolites outcropping in the Southeast Anatolian Orogenic Belt (Southeast of Turkey) mark the closure of the southern branch of the Neotethys Ocean associated with the collision between the Arabian Plate and Anatolian microplate. We present new geochemical, zircon U–Pb age, zircon Lu–Hf, and Sr-Nd isotopic data on the Southeast Anatolian Ophiolites to understand their formation ages, magma genesis, and geotectonic implications. The ophiolites, which are related to island arc igneous rocks, consist of mantle peridotites and crustal rocks (less dunite, gabbros, sheeted dykes, massive, and pillow basalts). The flat rare-earth element (REE) patterns, depletion in Nb and Ta, and enrichment in LILEs (Ba, Rb, Th, Sr, Pb) of gabbros suggest close similarities with very low Ti (boninitic) lavas found in the forearc regions. Using laser ablation inductively coupled plasma–mass spectrometry, zircon separated from leucogabbros, diabase dykes, and plagiogranites yield U-Pb ages of 92 and 83 Ma, which are interpreted to represent the formation ages of the ophiolites. The zircons in the gabbros and plagiogranites are dominated by positive εHf(t) values (between +3.1 and +?17.45) with a few negative εHf(t) values. High εHf(t) features are consistent with derivation from Mid-oceanic Ridge Basalt (MORB)-source mantle. The negative εHf(t) values of the zircons suggest the involvement of subducted sedimentary rocks. The southeast Anatolian ophiolites represent an SSZ-type ophiolite and are part of the Late Cretaceous oceanic lithosphere of the southern branch of the Neotethys Ocean that opened during the Late Triassic and closed during the Late Cretaceous.     

Geochronological and geochemical constraints on the petrogenesis of Early Eocene metagabbroic rocks in Nabang (SW Yunnan) and its implications on the Neotethyan slab subduction

Mafic rocks similar to those of the Gangdese belt have been poorly reported in the Nabang area (SW Yunnan Province in SW China) of the Eastern Himalayan Syntaxis. This led to a widely-accepted assumption that Early Eocene mafic rocks are absent in Nabang. This paper reports new zircon U–Pb, Lu–Hf isotopic, whole-rock elemental and Sr–Nd isotopic data for the recently identified Tongbiguan and Jinzhuzhai metagabbroic plutons. Our data show that the two mafic plutons crystallized at 53.2 ± 0.4 Ma and 53.6 ± 0.7 Ma, respectively, with zircon in-situ ε_Hf(t) values ranging from − 3.1 to + 4.9. Our data confirm the presence of Early Eocene mafic rocks in Nabang, contemporaneous with the major magmatic flare-ups of ~ 52 Ma in South Tibet. The rocks show high-K calc-alkaline basalt and basaltic andesite composition. They are characterized by subparallel spiky patterns with enrichment in LILEs, depletion in HFSEs and P–Ti negative anomalies. They show (Nb/La)n = 0.21–0.63, Ce/Pb = 2.99–9.91 and Nb/U = 5.2–14.1, along with high ⁸⁷Sr/⁸⁶Sr(t) ratios of 0.7061–0.7077 and ε_Nd(t) values of − 3.4 to − 5.6. Such geochemical signatures are similar to those of the synchronous Dangxung gabbroic and Yangbajing ultrapotassic rocks. Their least-contaminated samples can petrogenetically be attributed to input of slab-derived fluid into the lithospheric mantle. In conjunction with other available data, the mafic suite can be geochronologically and geochemically correlated to those in South Lhasa and are probably the equivalents of the Gangdese southeastward extension. Their formation might tectonically be related to slab rollback in response to the decreasing convergence rate. The termination of the Neotethyan subduction in SW Yunnan might be later than ~ 52 Ma, identical to that in South Tibet.     

Geological and geochemical constraints on the genesis of the Xiangquan Tl-only deposit,eastern China

The Xiangquan Tl deposit, located in the northern part of the Middle–Lower Yangtze Valley metallogenic belt, eastern China, is the only known Tl-only deposit. It is hosted in micritic limestone, marl and mudstone of the Lower Ordovician Lunshan Formation. The orebodies are controlled by the Xiao–Xiaolongwang–Dalongwang anticline and two reverse faults, and are generally stratabound and lenticular. Tl is only ore metal contained in disseminated, massive, brecciated and banded ores. The ore is composed of Tl-bearing pyrite, and gangue minerals quartz, fluorite, barite and carbonate. Alteration minerals include fluorite, barite, fine grained quartz and carbonate. Tl occurs isomorphously replacing iron in the lattice of pyrite, and less commonly as tiny independent Tl-bearing minerals which may be lafossaite (TlAsS₂) or lorandite (TlCl) appearing as 0.1–1 μm-sized cubic crystals. Xiangquan is a submarine sedimentary deposit and demonstrates that Tl, as a normally dispersed element, can form not only part of poly-metallic deposits but also as independent Tl deposits.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Chronological and geochemical constraints on the pre-variscan tectonic history of the Erzgebirge,Saxothuringian Zone

A combined U–Pb zircon geochronological and whole-rock isotopic and geochemical study has been carried out on high-grade orthogneiss, meta-basite, and meta-sediments from the Erzgebirge. The results indicate multiple pulses of Ediacaran–Ordovician magmatism in a transitional volcanic-arc to rift-basin setting. Orthogneiss from high-pressure nappes exhibit a step-like pattern of inherited zircon ages and emplacement ages of 500–475 Ma. In contrast, granite gneiss from the medium-pressure core of the Erzgebirge is characterised by three pulses of magmatism in the Early Cambrian, Late Cambrian, and Early Ordovician. A trend of decreasing Th/U ratios in zircon is observed to c.500 Ma, after which significant increases in the trend and variability of the data is inferred to mark the transition from arc-related to rift-related magmatism. Sediments deposited in the Early Cambrian have continental island arc affinity. Major detrital peaks in the Ediacaran and subordinate Tonian, Palaeoproterozoic, and Neoarchaean data are consistent with an Avalonian-Cadomian Arc and West African Craton derivation. The Early Cambrian sediments were locally reworked by a thermal event in the Ordovician resulting in leucocratic banding and recorded in Ordovician zircon rims characterised by systematically lower Th/U ratios. Ptygmatically folded leucocratic bands containing Ordovician zircon rims, associated with low Th/U ratios, are further observed in the granite gneiss core of the Erzgebirge. Variscan ages are rare, except in a fine-grained high-pressure micaschist, which contains exclusively small, structure-less, zircon with a weighted mean age of 350 ± 2 Ma. These data, along with a re-evaluation of previously published data, have been interpreted as the product of flattening subduction during the Early Cambrian; followed by the opening of slab windows in the Late Cambrian; and finally delamination in the Early Ordovician. Delamination of the orphaned slab led to asthenospheric upwellings triggering extension, bimodal magmatic pulses, recycling of fertile crust, high-temperature metamorphism, and cratonisation of relatively young crust.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

The role of microorganisms on the mineralogical and geochemical characteristics of the Parnassos-Ghiona bauxite deposits,Greece

The Parnassos-Ghiona bauxite deposits of Greece are hosted within carbonate rocks and have been formed during different geological ages. The most economically important deposits occur in the B3 bauxite horizon, which is developed over long distance as a continuous layer of 1–10 m in thickness, within Cretaceous limestones. Due to intense tectonics, a significant (approximately 30 vol.%) bauxite ores along and near their contact with faults show a brittle deformation and change in the color from red to black-gray, in a distance of tens of meter. Commonly gray to whitish bauxites are aluminum-enriched (> 65 wt.% Al₂O₃) and iron depleted.     

Hydroxamate siderophore-promoted reactions between iron(II) and nitroaromatic groundwater contaminants

Recent studies show that ferrous iron (Fe^II), which is often abundant in anaerobic soil and groundwater, is capable of abiotically reducing many subsurface contaminants. However, studies also demonstrate that Fe^II redox reactivity in geochemical systems is heavily dependent upon metal speciation. This contribution examines the influence of hydroxamate ligands, including the trihydroxamate siderophore desferrioxamine B (DFOB), on Fe^II reactions with nitroaromatic groundwater contaminants (NACs). Experimental results demonstrate that ring-substituted NACs are reduced to the corresponding aniline products in aqueous solutions containing Fe^II complexes with DFOB and two monohydroxamate ligands (acetohydroxamic acid and salicylhydroxamic acid). Reaction rates are heavily dependent upon solution conditions and the identities of both the Fe^II-complexing hydroxamate ligand and the target NAC. Trends in the observed pseudo-first-order rate constants for reduction of 4-chloronitrobenzene (k_obs, s⁻¹) are quantitatively linked to the formation of Fe^II species with standard one-electron reduction potentials, (Fe^III/Fe^II), below −0.3 V. Linear free energy relationships correlate reaction rates with the (Fe^III/Fe^II) values of different electron-donating Fe^II complexes and with the apparent one-electron reduction potentials of different electron-accepting NACs, (ArNO₂). Experiments describing a redox auto-decomposition mechanism for Fe^II-DFOB complexes that occurs at neutral pH and has implications for the stability of hydroxamate siderophores in anaerobic environments are also presented. Results from this study indicate that hydroxamates and other Fe^III-stabilizing organic ligands can form highly redox-active Fe^II complexes that may contribute to the natural attenuation and remediation of subsurface contaminants.     

Petrogenesis and tectonic implications of Early Cretaceous andesitic-dacitic rocks,western Qinling(Central China):Geochronological and geochemical constraints

~(40)Ar/~(39)Ar and zircon U-Pb geochronological and whole-rock geochemical analyses for the Laozanggou intermediate-acidic volcanic rocks from the western Qinling orogenic belt,Central China,constrain their petrogenesis and the nature of the Late Mesozoic lithospheric mantle.These volcanic rocks yield hornblende or whole-rock ~(40)Ar/~(39)Ar plateau ages of 128.3-129.7 Ma and zircon U-Pb age of131.3±1.3 Ma.They exhibit Si02 of 56.86-66.86 wt.%,K_2 O of 0.99-2.46 wt.% and MgO of 1.03-4.47 wt.%,with Mg# of 42-56.They are characterized by arc-like geochemical signatures with significant enrichment in LILE and LREE and depletion in HFSE.All the samples have enriched Sr-Nd isotopic compositions with initial ~(87)Sr/~(86)Sr ratios ranging from 0.7112 to 0.7149 and ε_(Nd)(t) values from 10.2 to 6.3.Such geochemical signatures suggest that these volcanic rocks were derived from enriched lithospherederived magma followed by the assimilation and fractional crystallization(AFC)process.The generation of the enriched lithospheric mantle is likely related to the modification of sediment-derived fluid in response to the Triassic subduction/collision event in Qinling orogenic belt.The early Cretaceous detachment of the lithospheric root provides a reasonable mechanism for understanding the petrogenesis of the Laozanggou volcanic sequence in the western Qinling orogenic belt.