Oxidative Ce3+ sequestration by fungal manganese oxides with an associated Mn(II) oxidase activity

Sequestration of Ce³⁺ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce³⁺ solution, newly formed BMOs exhibited stoichiometric Ce³⁺ oxidation, where the molar ratio of Ce³⁺ sequestered (Ce_seq) relative to Mn²⁺ released (Mn_rel) was maintained at approximately two throughout the reaction. A similar Ce³⁺ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN₃. Aerobic Ce³⁺ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce³⁺ sequestration over Mn²⁺ release, yielding Ce_seq/Mn_rel > 200, whereas heated or poisoned BMOs released a significant amount of Mn²⁺ with lower Ce³⁺ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn²⁺ release and enhanced oxidative Ce³⁺ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce³⁺ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce³⁺ oxidation at the solid phase produced through primary Ce³⁺ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce³⁺ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO₂ (CeO_2,BMO) showed faster auto-catalytic Ce³⁺ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce³⁺ oxidation on CeO_2,BMO was two orders of magnitude higher. Consequently, we concluded that Ce³⁺ contact with BMOs sequesters Ce³⁺ through two oxidation paths: primary Ce³⁺ oxidation by BMOs produces nano-sized crystalline cerianite, and subsequent auto-catalytic Ce³⁺ oxidation efficiently occurs using dissolved oxygen as the oxidizing agent. Pretreatment of newly formed BMOs with La³⁺ solution resulted in decreased rate constants for primary Ce³⁺ oxidation by BMO due to site blocking by La³⁺ sorption. The results presented herein increase our understanding of the role of BMO in oxidative Ce³⁺ sequestration process(es) through enzymatic and abiotic paths in natural environments and provide supporting evidence for the potential application of BMOs towards the recovery of Ce³⁺ from contaminated waters.     

Sorption and precipitation of Co(II) in Hanford sediments and alkaline aluminate solutions

Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO₂ resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O₂, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by ⁶⁰Co in the environment.     

Mineralogy of low grade metamorphosed manganese sediments of the Urals: Petrological and geological applications

The paper describes mineralogy of the low grade metamorphosed manganese sediments, which occur in sedimentary complexes of the Pai Khoi Ridge and the Polar Urals and volcanosedimentary complexes of the Central and South Urals. The degree of metamorphism of the rocks studied corresponds to PT conditions of the prehnite–pumpellyite (deposits of Pai Khoi and Polar and South Urals) and green schist (deposits of the Central Urals) facies. One hundred and nine minerals were identified in the manganese-bearing rocks on the basis of optical and electron microscopy, X-ray diffraction, and microprobe analysis. According to the variations in the amount of major minerals of the manganese rocks of the Urals, they are subdivided on carbonate (I), oxide–carbonate–silicate (II), and oxide–silicate (III) types. Carbonates, various Mn^2 +-bearing silicates associated with oxides and carbonates, and braunite (Mn^3 +-bearing silicate) are the major Mn hosts in types I, II, and III, respectively. Because of the different oxidation state of Mn, the rocks of types I and II are termed as “reduced” and the rocks of type III, as “oxidized”. The formation of a certain mineralogical type of metamorphic assemblage is controlled by the content of organic matter in the primary sediments. The sequence type I → type II → type III reflects the decrease in the amount of organic matter in metalliferous sediments. Mineralogical data indicate that manganese in the primary sediments accumulated in a silicate form (MnSi gel, glass, etc). During diagenesis, the Mn–Si phase was transformed to neotokite with subsequent formation of caryopilite and further crystallization of pyroxmangite, rhodonite, tephroite, and other silicates due to reactions involving caryopilite. The hydrated Mn-silicates (caryopilite and/or friedelite) and the spatially associated parsettensite, stilpnomelane, and other minerals are the index minerals of the low grade metamorphism. Under PT conditions of prehnite–pumpellyite facies, nearly 70% of silicate minerals are hydrous. The metamorphosed Mn-bearing sediments are characterized by the low-temperature caryopilite (or tephroite-caryopilite-pyroxmangite ± rhodonite) and the high-temperature caryopilite-free (or tephroite-pyroxmangite ± rhodonite) facies. Their PT conditions correspond to zeolite and prehnite-pumpellyite (the low-temperature) and green schist and higher grade (the high-temperature) facies.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.     

Using cocrystallization coefficients of isomorphous admixtures for determination of element concentrations in ore-forming solutions (by the example of Mn/Fe ratio in magnetite)

The cocrystallization coefficient of Mn and Fe (D_Mn/Fe) in magnetite crystals is determined in hydrothermal-growth experiments with internal sampling at 450 and 500 °C and 100 MPa (1 kbar). It is weakly dependent on temperature in the studied PT-region and is constant over a wide range of Mn/Fe values. This permits using the magnetite composition as an indicator of Mn/Fe in the fluid under equilibrium: (Mn/Fe)_aq ≈ 100 (Mn/Fe)_mt. Since Mn is often a macrocomponent of the fluid and a microcomponent of magnetite, local analysis of fluid inclusions for Mn might help to determine Fe even in iron minerals. This will permit evaluation of the contents of other ore metals if the D_Me/Fe values are known. For fine crystals (< 0.1–0.2 mm) with low contents of Mn (< 0.01–0.02%), it is necessary to take into account the fractionation of Mn into the surficial nonautonomous phase, in which its content can reach several percent. Comparison of these data with earlier data on the distribution of Mn in the system magnetite–pyrite–pyrrhotite–greenockite–hydrothermal solution shows that D_Mn/Fe remains constant in the presence of sulfur and sulfides. Precipitation of magnetite, in which Mn is a compatible admixture, cannot affect radically Mn/Fe in the solution because of the low D_Mn/Fe value. This effect is still more unlikely for pyrrhotite and pyrite, in which Mn is an incompatible admixture. The most probable mechanism of Mn fractionation into the solid phase is crystallization of FeOOH at lower temperatures. This is indirectly supported by the strong fractionation of Mn into the nonautonomous oxyhydroxide phase on the surface of magnetite crystals. The necessity of a more rigorous validation of “the new Fe/Mn geothermometer for hydrothermal systems” is substantiated.     

Chemical and physical properties of iron hydroxide precipitates associated with passively treated coal mine drainage in the Bituminous Region of Pennsylvania and Maryland

Changes in precipitate mineralogy, morphology, and major and trace element concentrations and associations throughout 5 coal mine drainage (CMD) remediation systems treating discharges of varying chemistries were investigated in order to determine the factors that influence the characteristics of precipitates formed in passive systems. The 5 passive treatment systems sampled in this study are located in the bituminous coal fields of western Pennsylvania and northern Maryland, and treat discharges from Pennsylvanian age coals. The precipitates are dominantly (>70%) goethite. Crystallinity varies throughout an individual system, and lower crystallinity is associated with enhanced sorption of trace metals. Degree of crystallinity (and subsequently morphology and trace metal associations) is a function of the treatment system and how rapidly Fe(II) is oxidized, forms precipitates, aggregates and settles. Precipitates formed earlier in the passive treatment systems tend to have the highest crystallinity and the lowest concentrations of trace metal cations. High surface area and cation vacancies within the goethite structure enable sorption and incorporation of metals from coal mine drainage-polluted waters. Sorption affinities follow the order of Zn > Co ≈ Ni > Mn. Cobalt and Ni are preferentially sorbed to Mn oxide phases when these phases are present. As pH increases in the individual CMD treatment systems toward the pH_pzc of goethite, As sorption decreases and transition metal (Co, Mn, Ni and Zn) sorption increases. Sulfate, Na and Fe(II) concentrations may all influence the sorption of trace metals to the Fe hydroxide surface. Results of this study have implications not only for solids disposal and resource recovery but also for the optimization of passive CMD treatment systems.     

Arsenic attenuation in geothermal streamwater coupled with biogenic arsenic(III) oxidation

In the present study, we investigated As behavior in a high-As hot spring (Sambe hot spring, Shimane, Japan) by coupling direct chemical speciation by synchrotron-based XAFS and HPLC–ICP-MS with microbial As-redox transformation gene analysis. The concentration of soluble As in the spring streamwater decreased immediately along the flow in correlation with Fe behavior, indicating that As in the streamwater was naturally attenuated in the streamwater. Iron XAFS analysis suggested deposition of Fe(III) oxyhydroxides along the flow. Thus, considering the strong affinity of As to Fe oxyhydroxides, the observed attenuation in As was possibly caused by sorption (or incorporation) of As on Fe(III) oxyhydroxides. Both dissolved As(III) and As(V) were present in the aqueous phase, and As(III) was rapidly oxidized to As(V) (<30 s) along the flow. The oxidation kinetics indicated the occurrence of biotic As(III) oxidation, because obtained As(III) oxidation rate (6.7–7.8 μM min⁻¹) was much faster than the reported abiotic oxidation rates. Furthermore, the bacterial arsenite oxidase gene (aioA) was detected in DNA extracted from all samples (average of 2.0 × 10⁵ copies dry g⁻¹), which also supported potential attributes of biological As(III) oxidation in situ. In solid phase samples from sampling points analyzed by XAFS, most of the As existed as oxidized pentavalent form, As(V). This result indicated that this form was preferentially partitioned to the solid phase because of the much higher affinity of As(V) than of As(III) to Fe(III) oxyhydroxides. Considering the kinetic and microbiological findings, it is indicated that biotic process was predominantly responsible for As(III) oxidation at the present site, and this biotic As(III) oxidation to As(V) controlled the observed attenuation of As, because oxidized As(V) was removed from the aqueous phase by Fe(III) oxyhydroxides more efficiently.     

The age of supergene manganese deposits in Katanga and its implications for the Neogene evolution of the African Great Lakes Region

Supergene manganese deposits commonly contain K-rich Mn oxides with tunnel structure, such as cryptomelane, which are suitable for radiometric dating using the ³⁹Ar–⁴⁰Ar method. In Africa, Mn deposits have been dated by this method for localities in western and southern parts of the continent, whereas only some preliminary data are available for Central Africa. Here we present new ³⁹Ar–⁴⁰Ar ages for Mn oxide samples of the Kisenge deposit, in southwestern Katanga, Democratic Republic of the Congo. The samples represent supergene Mn oxide deposits that formed at the expense of primary Paleoproterozoic rhodochrosite-dominated carbonate ores. Main phases of Mn oxide formation are dated at c. 10.5 Ma, 3.6 Ma and 2.6 Ma for a core that crosses a mineralized interval. The latter shows a decrease in age with increasing depth, recording downward penetration of a weathering front. Surface samples of the Kisenge deposits also record a ≥ c.19.2 Ma phase, as well as c. 15.7 Ma, 14.2 Ma and 13.6 Ma phases. The obtained ages correspond to distinct periods of paleosurface development and stability during the Mio-Pliocene in Katanga. Because Katanga is a key area bordered to the North by the Congo Basin and to the East by the East African Rift System, these ages also provide constraints for the geodynamic evolution of the entire region. For the Mio-Pliocene, the Kisenge deposits record ages that are not systematically found elsewhere in Africa, although the 10.5–11 Ma event corresponds to a roughly simultaneous event in the Kalahari Manganese Field, South Africa. The rest of the Katanga paleosurface record differs somewhat from records for other parts of Africa, for which older, Eocene ages have been obtained. This difference is most probably related to the specific regional geodynamic context: uplift of the East African Plateau, with associated erosion, and the opening of the East African Rift System at c. 25 Ma are events whose effects, in the study area, interfere with those of processes responsible for the development of continent-wide paleosurfaces.     

Critical metals in manganese nodules from the Cook Islands EEZ,abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km² and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO₂ and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9 mm/10⁶ years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45 kg/m²) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m². Six ~ 20,000 km² areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (> 25 kg/m² over ~ 123,844 km²), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.     

Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti,REE) deposit (Amazonas,Brazil)

The Morro dos Seis Lagos niobium deposit (2897.9 Mt at 2.81 wt% Nb₂O₅) is associated with laterites formed by the weathering of siderite carbonatite. This iron-rich lateritic profile (>100 m in thickness) is divided into six textural and compositional types, which from the top to the base of the sequence is: (1) pisolitic laterite, (2) fragmented laterite, (3) mottled laterite, (4) purple laterite, (5) manganiferous laterite, and (6) brown laterite. All the laterites are composed mainly of goethite (predominant in the lower and upper varieties) and hematite (predominant in the intermediate types, formed from goethite dehydroxylation). The upper laterites were reworked, resulting in goethite formation. In the manganiferous laterite (10 m thick), the manganese oxides (mainly hollandite, with associated cerianite) occur as veins or irregular masses, formed in a late event during the development of the lateritic profile, precipitated from a solution with higher oxidation potential than that for Fe oxides, closer to the water table. Siderite is the source for the Mn. The main Nb ore mineral is Nb-rich rutile (with 11.26–22.23 wt% Nb₂O₅), which occurs in all of the laterites and formed at expense of a former secondary pyrochlore, together with Ce-pyrochlore (last pyrochore before final breakdown), Nb-rich goethite and minor cerianite. The paragenesis results of lateritization have been extremely intense. Minor Nb-rich brookite formed from Nb-rich rutile occurs as broken spherules with an “oolitic” (or Liesegang ring structure). Nb-rich rutile and Nb-rich brookite incorporate Nb following the [Fe³⁺ + (Nb, Ta) for 2Ti] substitution and both contain up to 2 wt% WO₃. The laterites have an average Nb₂O₅ content of 2.91 wt% and average TiO₂ 5.00 wt% in the upper parts of the sequence. Average CeO₂ concentration increases with increasing depth, from 0.12 wt% in the pisolitic type to 3.50 wt% in the brown laterite. HREE concentration is very low.     

The Diavik waste rock project: Initial geochemical response from a low sulfide waste rock pile

Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L⁻¹ when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L⁻¹ (as total CaCO₃), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L⁻¹, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L⁻¹), Ni (<7.0 mg L⁻¹), Co (<1.5 mg L⁻¹), Zn (<0.5 mg L⁻¹), Cd (<0.008 mg L⁻¹) and Cu (<0.05 mg L⁻¹) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe_1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS₂] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO₄, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock.     

Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic)

Thick ferromanganese (Fe-Mn) crusts from four Cretaceous seamounts (The Paps, Tropic, Echo and Drago) at the southern Canary Island Seamount Province (CISP) in the northeastern tropical Atlantic were recovered along the flanks and summits from 1700 to 3000 m water depths. CISP is composed of > 100 seamounts and submarine hills, is likely the oldest hotspot track in the Atlantic Ocean, and is the most long-lived of known hotspots globally. The Fe-Mn crusts grow on basalt-sedimentary rock substrates below the northeastern tropical Atlantic core of the oxygen minimum zone (OMZ) with a maximum thickness of 250 mm at a water depth of 2400 m. The mineralogical and chemical composition of these Fe-Mn crusts indicate a hydrogenetic origin. The main Mn minerals are vernadite with minor interlayered todorokite and asbolane-buserite. Fe oxides are essentially ferroxyhyte and goethite. The Fe-Mn crusts show high average contents in Fe (23.5 wt%), Mn (16.1 wt%), and trace elements like Co (4700 μg/g), Ni (2800 μg/g), V (2400 μg/g) and Pb (1600 μg/g). Rare earth elements plus yttrium (REY) averages 2800 μg/g with high proportions of Ce (1600 μg/g). Total platinum group elements (PGEs) average 230 ng/g, with average Pt of 182 ng/g. Two main types of growth layers form the crusts: 1) a dense laminae of oxides with high contents in Mn, Co and Ni associated with vernadite and Cu, Ni, and Zn associated with todorokite; 2) botryoidal layers with high contents in Fe, Ti, V and REY associated with goethite. The Fe-Mn crusts from the CISP region show higher contents in Fe, V, Pb and REY but lower Mn, Co, Ni and PGEs contents than Pacific or Indian ocean seamount crusts. The oldest maximum age of initiation of crust growth was at 76 Ma (Campanian, Late Cretaceous). Using a combination of high resolution Co-chronometer and geochemical data along an Electron Probe Micro Analysis (EPMA) transect, four stages in morphology, chemical contents and growth rates can be differentiated in the the Cenozoic crusts since 28 Ma, which we interpret as due to changes in the ventilation of the North Atlantic OMZ and to the increase of Saharian dust inputs. An earliest growth period, characterized by similar contents of Fe and Mn in the interval 27.8–24.45 Ma (late Oligocene-early Miocene) reflects slow precipitation related to a thick OMZ. An intermediate laminated zone with higher contents of Fe, Si and P, high growth rates reaching 4.5 mm/Ma, and precipitation of Fe-Mn oxides during the interval 24.5–16 Ma is related to periods of ventilation of the OMZ by intrusion of deep upwelling currents. Significant increase in Fe contents at ca. 16 Ma correlates with the onset of incursions of Northern Component Waters into the North Atlantic. Finally, since 12 Ma, the very low growth rates (< 0.5 mm/Ma) of the crust are related to a thick North Atlantic OMZ, an increase in Sahara dust input and a stable thermohaline circulation.     

The oxidation of cobalt(II) adsorbed on manganese dioxide

X-ray photoelectron spectroscopy (XPS) measurements of cobalt adsorbed on MnO₂ reveal strong evidence that Co(II) has been oxidized to Co(III). The manganese spectra are characteristic of Mn(IV). Model calculations suggest that Co(II) cannot be oxidized by O₂ to Co(III) in bulk solution at seawater concentrations but that the oxidation can proceed in the presence of the strong electric field at the MnO₂-solution interface. Ni(II), however, cannot be oxidized at the interface except at very high concentrations. These calculations suggest that the oxidation of Co(II) can explain the geochemical separation of cobalt from nickel.     

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples.Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5–4) or near neutral (pH 6–7); ≈ 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6.The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze.The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO₂ and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= −net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of Fe^II/Fe^III. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples.A meaningful “net” acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinity_measured − Hot Acidity_measured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H⁺ acidity and is not recommended. The use of net alkalinity = −Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinity_measured − Acidity_calculated) is recommended with some cautions.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

New geochemical and mineralogical constraints on the genesis of the Vani hydrothermal manganese deposit at NW Milos island,Greece: Comparison with the Aspro Gialoudi deposit and implications for the formation of the Milos manganese mineralization

The Mn-Ba-Pb deposit at Aspro Gialoudi in NW Milos is shown to be a fossil inhalative-exhalative hydrothermal deposit that represents the deepest part of the Vani succession at the western extremity of the main Vani manganese deposit. The geology of the Vani-Aspro Gialoudi area is characterized by Upper Pliocene-Lower Pleistocene dacitic and rhyodacitic lava domes, which are overlain by the Vani volcaniclastic unit considered to be part of the 2.66–1.44 Ma magmatic event at Milos Island. The presence of in-situ and intrusive hyaloclastite breccias surrounding the coherent lava domes at Aspro Gialoudi and Vani areas indicates submarine emplacement for the domes. The dacitic-rhyodacitic domes are variously altered (mainly propylitic and/or argillic alteration, silicified and in some cases locally exhibiting adularia alteration). Both Aspro Gialoudi and main Vani deposit are located proximal to fault systems: the main Vani manganese deposit is adjacent to the NW-trending Kondaros-Katsimouti-Vani Dome fault, whereas the Aspro Gialoudi deposit is adjacent to the relatively minor NE-trending fault on the west coast of Milos. At Aspro Gialoudi, mineralization took place in a subseafloor and/or seafloor environment and is characterized by a stratabound Mn-barite-rich deposit mainly within a package of propylitized intrusive hyaloclastites and within the overlying sandstones. Banded epithermal veins trending NE-SW and composed of chalcedonic silica/quartz + barite + Mn-oxide ± sulfides crosscut the dacitic lavas, the hyaloclastites and the overlying volcaniclastic sequence at Aspro Gialoudi and are considered to represent the feeder zones of the manganese-barite mineralization. Within the veins, early sulfide (galena-sphalerite) barite and quartz deposition is followed by manganese oxides and aragonite, thus resembling the epithermal-style Pb-Zn-Ag-Mn mineralization across the NW-trending Katsimoutis-Kondaros-Vani fault. Mineralization in Aspro Gialoudi and Vani deposits seems to be controlled by alternating cycles of deposition of sulfides and hydrothermal manganese oxides within the faults. Manganese deposition in both deposits formed in a similar manner, namely by transport of hydrothermal fluids through the adjacent fault systems into a reservoir of volcanoclastic sandstone and hyaloclastites to produce a deposit initially consisting of principally of pyrolusite and occasionally ramsdellite, which were subsequently replaced by cryptomelane, hollandite, coronadite and hydrohaeterolite. Precipitation of hydrothermal manganese oxides took place very quick and under microbial Mn(II) oxidation. Compositional data show that metallic elements most enriched in the Aspro Gialoudi and Vani manganese deposits relative to the average continental crust, lie in the sequences Pb > Cd > Mn > As > Sb > Zn > W > Tl > Ba > Cu > Mo > Co > Bi and As > Sb > Pb > Mn > Tl > Cd > Zn > W > Cu > Ba > Mo > Co, respectively. Mineralogical and geochemical (e.g. REE) data from both Aspro Gialoudi and main Vani deposit are taken to indicate mainly a seawater source for the hydrothermal fluids. These two deposits are genetically and spatially related to base- and precious metal intermediate-sulfidation epithermal mineralization. They formed successively by similar processes and are considered to be integral parts of the same hydrothermal system.     

Sequential extraction of labile elements and chemical characterization of a basaltic soil from Mt. Meru,Tanzania

We conducted a modified Bureau Commun Reference (BCR) sequential extraction on a basaltic soil (phono-tephrite) from Mt. Meru in Northern Tanzania in order to determine the relative contribution of water soluble, carbonate and exchangeable, oxide and organic fractions to the bulk composition of the soil. Elemental compositions were determined by ICP-MS and corrected for loss on ignition. Relatively immobile elements, such as Zr, Hf and Al, are enriched by 10–30% compared to the unweathered protolith, consistent with soil formation being accompanied by mass loss due to chemical weathering. However, superimposed on this mass loss appears to be enrichment of elements such as Fe, Ca and Mg, especially towards the surface. In some cases, the bulk concentrations of these elements at the surface exceed that of the protolith. These data suggest that the surface of the Meru soil columns may have experienced “re-fertilization” by the deposition of volcanic ash. From the carbonate and exchangeable extraction, we found evidence of clay rich horizons which may sequester as much as 5% of the bulk K. The concentration of calcium carbonate appears to decrease with depth, but the largest incorporation of Sr and Ba into carbonates occurs below 114 cm. Fe and Mn oxides scavenge more than 10–20% of total Ti, V, Co, Cu, Zr and Pb below 114 cm. The organic fraction sequestered significant fractions of total Al, Cu, REE’s and Pb throughout the soil column.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.