Mn-oxide: a major source of easily mobilisable Co and Ni under reducing conditions in New Caledonia FerralsolsLes oxydes de Mn : une source majeure de Co et Ni facilement mobilisables en conditions réductrices dans les Ferralsols de Nouvelle-Calédonie

Chemical and bacterial reduction and dissolution of Fe and Mn-oxide and the concomitant solubilisation of Co and Ni were studied in a surface horizon of a New-Caledonia Ferralsol. Chemical extractions showed that Mn and Co were in a large part associated in Mn-oxides. The main part of Ni was associated with goethite, but a very small fraction was also associated with Mn-oxides. Anaerobic reducing bacterial activity was responsible for Fe solubilisation at a smaller extent than for Mn solubilisation and consequently for associated metal release. Submicroscopic investigations revealed the presence of a Mn-oxide containing Co, Ni and Al, close to a lithiophorite–asbolane mixed-layers Mn-oxide, which can be considered as a main source of easily available metals in this soil. To cite this article: C. Quantin et al., C. R. Geoscience 334 (2002) 273–278.     

Oxidation of Mn(II): Initial mineralogy,oxidation state and ageing

The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), $\text{O}\text{Mn}$ ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn₃O₄ (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The $\text{O}\text{Mn}$ ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn₃O₄ to γMnOOH but not to γMnO₂.     

A kinetic approach to describe trace-element distribution between particles and solution in natural aquatic systems

The partitioning of radioactive trace elements between seawater and particulate matter from surface sediments and sediment traps was investigated in laboratory experiments. For the elements Na, Zn, Se, Sr, Cd, Sn, Sb, Cs, Ba, Hg, Th and Pa (group I) constant distribution coefficients (K_d) were found after a few days of equilibration, whereas the elements Be, Mn, Co and Fe (group II) showed an increasing K_d over the whole time of observation of 108 days. The time dependence of K_d is described by an adsorption-desorption equilibrium (group I elements), followed by a lattice transport reaction step (group II elements). The reaction rate constants are compared to Mn oxidation rates and to adsorption rate constants derived from in situ measurements of the $\text{U}\text{Th}$ disequilibrium as available from literature.     

The major-element chemistry of suspended matter in the Amazon Estuary

Suspended matter from the surface waters of the Amazon Estuary were collected during May and June 1976 on the ‘R/V Alpha Helix’, and their major-element compositions (Al, Si, Ti, K, Mg, Ca, P, Fe and Mn) were measured.Between salinities of 0 and 10%. the suspended material, predominantly terrigenous in derivation, decreases in load from 500 to 3 mg/l, but has a chemical composition which remains essentially constant. With the onset of a large amount of biological productivity at approximately 10%. salinity, there are large increases in the ratios of $\text{Si}\text{Al}$, $\text{P}\text{Al}$, $\text{Ca}\text{Al}$, $\text{Mg}\text{Al}$, $\text{Ti}\text{Al}$ and $\text{Mn}\text{Al}$ which are maintained at higher salinities. Calculations of “excess” concentrations of elements held in the non-terrigenous components of the suspended material further support our main conclusion that Si, P, Ca, Mg, Ti and Mn are incorporated into the skeletal and organic phases of marine phytoplankton (predominately diatoms) of the Amazon Estuary. The data suggest, but with less certainty, that Fe and K follow the above elements.This study has demonstrated that the chemical composition of river-introduced suspended matter can be significantly altered by biological activity within estuarine waters as can be the geochemical cycle of inorganic elements.     

Organic geochemistry of suspended and settling particulate matter in Lake Michigan

Organic matter contained in particulate matter in Lake Michigan waters and sediments has been characterized by $\text{C}\text{N}$ ratios and by distributions of biomarker fatty acids, alkanols, sterols, and aliphatic hydrocarbons. Differences in organic constituents of particulate matter from various depths and distances from shore indicate a complex interaction of production, transformation, and destruction of the organic matter contained in sinking particles. Near-surface material contains important contributions of landderived organic matter, presumably of eolian input. Midwater particles have predominantly aquatic organic material of algal origin. At the sediment-water interface, selective suspension of the finer fractions of surficial sediments enriches bottom nepheloid layers with these sediment size classes. As a result, near-bottom particulate matter has an aquatic biomarker character. Organic matter associated with sinking particles undergoes substantial degradation during passage to the bottom of Lake Michigan, and aquatic components are selectively destroyed relative to terrigenous components.     

Erosion of particulate inorganic and organic matter in the Gulf of LionÉrosion de la matière particulaire inorganique et organique dans le golfe du Lion

Critical shear stress of erosion and erosion rate of particulate inorganic and organic matter were measured in a flume at three muddy stations. Critical shear stress ranged between 0.022 and $\text{0.038 }\text{N}\text{m}{}^{\mathrm{?2}}$. At the deepest site, annual erosion of particulate organic nitrogen and phosphorus could exceed net deposition fluxes, showing the importance of erosion processes. Erosion may modify total system mineralisation rates by introducing sedimentary particulate organic matter into the water column and thus this process must be taken into account in studies of biogeochemical cycles. To cite this article: E. Schaaff et al., C. R. Geoscience 334 (2002) 1071–1077.     

Temperature dependence of Mn(II) oxidation in lakewaters: a test of biological involvement

The oxidation rates of Mn(II) in water samples from two English lakes, Esthwaite Water and Rostherne Mere, display clear temperature optima, varying from 15°C to 30°C, in the pH range 7–8. This is strong evidence of biological mediation of the oxidation. The types and concentrations of Mn-oxidising organisms appear to vary with depth and time in both lakes.     

Storage of F and Cl in the upper mantle: geochemical implications

Electron microprobe analyses yielded mean values of $\text{F}\text{0.43}\text{and}\text{Cl}\text{0.08}\text{wt.}\text{\%}$ for primary-textured phlogopites in coarse, depleted garnet-lherzolite xenoliths from kimberlites. Most secondary-textured phlogopites have too low Cl (0.01–0.08 wt.%) to be metamorphic precursors of primary-textured phlogopites. MARID-suite phlogopites and many megacrysts in kimberlites have low Cl ($\text{～ 0.02}\text{wt.}\text{\%}$), and some but not necessarily all secondary micas may result from infiltration of kimberlite into peridotite xenoliths. A good correlation between P and F in some oceanic basalts and gabbros might suggest that these elements are derived mainly from F-rich apatite inthe mantle, and that whitlockite is not present in the source region. Mantle-derived mica and amphibole have such low Cl that it is necessary to attribute Cl in oceanic basalts and gabbros either to substantial Cl in the source apatite, or to Cl from invading solutions, or both: three apatites from the mantle contain 0.8–1.0 wt.% Cl, and others contain lower amounts. The halogen contents of kimberlitic magmas can be explained by incorporation of Cl-bearing mica and F-rich apatite during melting of peridotites, but compositional constraints are weak.     

Characterization of manganese oxide precipitates from Appalachian coal mine drainage treatment systems

The removal of Mn(II) from coal mine drainage (CMD) by chemical addition/active treatment can significantly increase treatment costs. Passive treatment for Mn removal involves promotion of biological oxidative precipitation of manganese oxides (MnO_x). Manganese(II) removal was studied in three passive treatment systems in western Pennsylvania that differed based on their influent Mn(II) concentrations (20–150 mg/L), system construction (±inoculation with patented Mn(II)-oxidizing bacteria), and bed materials (limestone vs. sandstone). Manganese(II) removal occurred at pH values as low as 5.0 and temperatures as low as 2 °C, but was enhanced at circumneutral pH and warmer temperatures. Trace metals such as Zn, Ni and Co were removed effectively, in most cases preferentially, into the MnO_x precipitates. Based on synchrotron radiation X-ray diffraction and Mn K-edge extended X-ray absorption fine structure spectroscopy, the predominant Mn oxides at all sites were poorly crystalline hexagonal birnessite, triclinic birnessite and todorokite. The surface morphology of the MnO_x precipitates from all sites was coarse and “sponge-like” composed of nm-sized lathes and thin sheets. Based on scanning electron microscopy (SEM), MnO_x precipitates were found in close proximity to both prokaryotic and eukaryotic organisms. The greatest removal efficiency of Mn(II) occurred at the one site with a higher pH in the bed and a higher influent total organic C (TOC) concentration (provided by an upstream wetland). Biological oxidation of Mn(II) driven by heterotrophic activity was most likely the predominant Mn removal mechanism in these systems. Influent water chemistry and Mn(II) oxidation kinetics affected the relative distribution of MnO_x mineral assemblages in CMD treatment systems.     

Biogeochemistry of manganese oxide coatings on pebble surfaces in the Kikukawa River System,Shizuoka, Japan

The biogeochemistry of Mn-oxide coatings formed over submerged pebble surfaces on the streambed of the Kikukawa river system has been investigated. Located in central Shizuoka, Japan, this system drains strongly acidified soils under tea plantations. Besides containing high amounts of Mn (up to 450 μg/cm²), the coatings are capable of scavenging and accumulating other elements including Ba, Zn, Ni, Co, W, Mo and Sb. When suspensions of the coating material were incubated with 0.2 mM Mn²⁺, the Mn(II) ion was microbially transformed into Mn-oxides. When the same suspensions were spread on agar plates containing acetate, yeast-extract, and 1.0 mM Mn²⁺ (AY agar medium) both Mn-oxidizing bacteria and fungi appeared, indicating the existence of a diversity of Mn-oxidizing microorganisms in the system. Plate counts using two agar culture media with varied nutrient levels indicated that the ability of these microorganisms to oxidize Mn(II) was strongly dependent on nutrient supply. The relatively nutrient-poor AY agar medium was more conducive to microbial growth than the K₁ agar medium with a higher organic nutrient content. Concentrations of Mn dissolved in the stream waters did not correlate well with the amounts of solid Mn on submerged pebbles. Thus, factors other than dissolved Mn concentration (e.g., organic nutrient supply and pH) determined the ability of microorganisms to oxidize Mn in the streambeds. A survey of dissolved Mn in streams and water draining tea plantations combined with chemical analysis of Mn in the underlying soils indicate that the soils have been strongly acidified through excessive applications of N-fertilizers. As a result, Mn was leached from the soil column into the Kikukawa river system. Biogenic Mn-oxide coatings on streambeds can therefore serve as an indicator of soil acidification and metal leaching from soils of the corresponding watershed.     

Kinetic and thermodynamic factors controlling manganese concentrations in oceanic waters

Data are presented describing the changes in the distribution of dissolved and particulate Mn observed over a 16-month period in the periodically anoxic waters of Saanich Inlet, a fjord located on the coast of Vancouver Island, British Columbia. During the spring and summer when the bottom waters were anoxic, a dense cloud of particulate Mn was found at mid-depths where Mn²⁺ enriched anoxic bottom waters were mixing with oxygenated waters; then, during the autumn aand winter following an intrusion which reoxygenated the bottom water, an intense precipitation of Mn was observed throughout the entire water column. During this latter period, dissolved Mn concentrations in the bottom water, which exceeded 1000 nmol/l under anoxic conditions, decreased towards a lower limit of 1.6 nmole/l, a value comparable to that observed in Pacific Ocean waters of similar pH and dissolved oxygen content. Mn in the particulate matter collected just above the oxic-anoxic interface was found to have an average oxidation number of +3.05; and, on this basis, it is proposed that dissolved Mn concentrations in oceanic waters are controlled by the precipitation of the metastable oxide mineral manganite (γ-MnOOH), a hypothesis consistent with the fact that dissolved Mn values in subsurface Pacific Ocean waters closely approach the equilibrium solubility of this phase. Temporal and spatial gradients in the particulate Mn distribution were used to calculate the in situ rate of Mn precipitation, and the results of these calculations then were fitted to theoretical rate equations which suggest that the precipitation of Mn is controlled by 2 parallel processes: bacterial oxidation and an inorganic autocatalytic oxidation reaction.     

Manganese(II) oxidation driven by lateral oxygen intrusions in the western Black Sea

Mn(II) oxidation in the suboxic zone of the water column was studied at four stations in the western Black Sea. We measured Mn(II) oxidation rates using ⁵⁴Mn tracer and tested the hypothesis of alternative oxidants for Mn(II) other than dissolved oxygen. In anoxic incubation experiments with water from different depths of the chemocline, Mn(II) was not oxidized by nitrite, nitrate, or iodate. In the presence of light, Mn(II) also was not oxidized under anoxic conditions as well. Anaerobic Mn(II) oxidizing microorganisms could not be enriched. In oxic incubation experiments, the addition of alternative oxidants did not significantly increase the Mn(II) oxidation rate. The lack of an anaerobic Mn(II) oxidation in our experiments does not unambiguously prove the absence of anaerobic Mn(II) oxidation in the Black Sea but suggests that dissolved oxygen is the only oxidant for biologically catalyzed Mn(II) oxidation. Lateral intrusions of modified Bosphorus water were shown to be the main mechanism providing dissolved oxygen in the suboxic and the upper anoxic zones and explaining observed Mn(II) oxidation rates. Maximum in situ Mn(II) oxidation rates in the suboxic zone were 1.1 nM Mn(II) per h in the central Black Sea, 25 nM Mn(II) per h on the Romanian continental slope and 60 nM Mn(II) per h on the Anatolian continental slope. These rates correlate with the amount of particulate Mn and the number of Mn-oxide particles and are in agreement with rates measured 13 yr before. Our study highlights the importance of lateral intrusions of oxygen for the ventilation of the suboxic zone and the anoxic interior and for the regulation of different oxidation-reduction processes in the chemocline, including Mn(II) oxidation, which may be significant for other anoxic basins as well.     

The chemistry of suspended matter in Esthwaite Water,a biologically productive lake with seasonally anoxic hypolimnion

Ten detailed vertical water column profiles were taken between April and November, 1979, in Esthwaite Water (English Lake district), a lake with high biological productivity and a seasonally anoxic hypolimnion. Measurements of the major-element particle composition (organic C, P, S, Si, Al, Ti, K, Mg, Ca, Fe, Mn, and Ba) and hydrochemical constituents (temperature, pH, dissolved oxygen, total suspended load, dissolved Fe, Mn, P, and Ba) were carried out. These have revealed new information about the mechanisms and kinetics of biogeochemical cycles in a lake.Pronounced seasonal cycles exist in which large excess concentrations (those unsupported by detrital components) of particulate organic C, Fe, Mn, P, S, Mg, K, Ba, and Ca are being generated and lost in situ in the water column (15m deep). In the epilimnion these elements (excepting Fe and Mn) are incorporated into the organic components of growing phytoplankton during the spring and summer. Simultaneously, in the hypolimnion there is a build-up and then a decrease in the excess concentrations of particulate C, P, S, Mg, K, Ba and Ca; this cycle is due to the indirect involvement of these elements with the iron redox cycle. As the hypolimnion becomes anoxic, dissolved ferrous Fe is released from the sediments and large concentrations of excess particulate iron (III) oxides accumulate; these oxides act as adsorbing substrates for the above mentioned elements. As conditions become more reducing, these same elements are solubilized as the iron (III) oxide particles are reduced to dissolved ferrous iron.Adsorption equations are derived from the field data which relate the concentration of excess particulate Fe to those of POC, P, S, Ca, Mg, Ba, and K. At the last stages of anoxia (before the lake overturns) large populations of bacteria and the formation of iron sulfide particles control the concentrations of excess particulate C, S, P, Mg, K, and Ca.     

Orthopyroxene-olivine assemblages in diogenites and mesosiderites

Diogenites contain equilibrated orthopyroxene-olivine assemblages. Mn is very regularly partitioned between olivine and orthopyroxene in pallasites, diogenites and synthetic eucrite melts, with an $\text{FeO}\text{MnO}$ partition ratio for olivine versus orthopyroxene of 1.6 by weight over a very wide range of FeO contents. In contrast to diogenites, Fe and Mn are not regularly partitioned between the olivine and orthopyroxene of mesosiderites and these minerals were not in equilibrium. Mesosiderite olivine differs from diogenite olivine in $\text{Fe}\text{Mn}$ and $\text{Ca}\text{Mn}$ ratios. Lack of olivine-orthopyroxene equilibrium suggests that olivine in mesosiderites was derived not from a pyroxenite component analogous to diogenites but from dunites.     

Stenols and stanols in the oxic and anoxic waters of the Black Sea

Water samples collected from a slope station and two deep stations in the western basin of the Black Sea were analyzed for stenols and stanols by glass capillary gas chromatography. These results were used in conjuction with hydrographic, particulate organic carbon, and chlorophyll a data to better understand sterol sources and their transport and transformation mechanisms in anoxic basins.The total free sterol concentrations found in the surface waters were 450–500 ng/l dropping rapidly to values well below 100 ng/l at depths below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the upper 200 m of the water column a strong association of sterols with particulate matter is suggested. Structural elucidation by a gas chromatograph-mass spectrometer-computer system revealed the presence of at least sixteen different stenols and stanols in the surface waters of the Black Sea. Cholesterol, 24-methylenecholesterol and 24-methylcholesta-5,22-dien-3β-ol were the major sterols in the surface waters. Cholesterol and 24-ethylcholesterol both exhibited a subsurface maximum at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the anoxic deep waters (200–2000 m) only cholesterol and 24-ethylcholesterol were found. Two stenols were found that have not been reported in seawater: a C₂₆ stenol with a saturated C₇H₁₅ side chain (presumably 24-norcholesterol) and 24-ketocholesterol. At least six 5α-stanols could be identified in the surface samples, each of them comprising about 10–20% of the concentration of the corresponding Δ5-stenol. From these comparatively high surface values the stanol concentrations drop rapidly to values near zero at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Except for very low concentrations of 5α-cholestanol (< 4ng/l) no other stanols could be detected in the anoxic zone.From this data it appears that no detectable stenol → stanol conversion is occurring at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface or in the deep anoxic waters of the Black Sea.     

The oxidation state of manganese in marine sediments and ferromanganese nodules

Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the $\text{O}\text{Mn}$ ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had $\text{Mn}\text{Fe}$ ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with $\text{O}\text{Mn}$ values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized ($\text{O}\text{Mn}\text{= 1.90 to 2.00}$) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the $\text{O}\text{Mn}$ ratio in the solid phase decreases. The $\text{O}\text{Mn}$ ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO₃ formation can not be ruled out in all cases.     

Volatile contents and ferric-ferrous ratios of basalt,ferrobasalt, andesite and rhyodacite glasses from the Galapagos 95.5°W propagating rift

Volatiles and major elements in abyssal glasses ranging in composition from basalt, ferrobasalt, andesite to rhyodacite from the Galapagos Spreading Center (GSC) near 95°W were analyzed using electron microprobe and high temperature mass spectrometry. Total volatile content ranged from 0.32 wt.% to 2.74 wt.%. Volatile abundances of MORB glasses from the 95.5°W propagating rift are similar to those from the adjacent normal rift (avg. 0.34 wt.%) and lower than those of N-type MORB from the Mid-Atlantic Ridge (avg. 0.49 wt.%). Although both propagating and non-propagating rift glasses contain trace amounts of methane (<0.01 wt.%) and carbon monoxide (0.04 wt.%), significantly higher 100 $\text{Fe}{}_2\text{O}{}_3\text{FeO}\text{+ Fe}{}_2\text{O}{}_3$ ratios are observed for the primitive propagating rift glasses. Water contents of the most primitive GSC glasses are ~0.09 wt.% suggesting a water content for the mantle source of ~0.02 wt.% which indicates that source masses with very low water content can be involved in the generation of MORB.In fractionated ferrobasalt, andesite and rhyodacite glasses from the 95.5°W propagating rift, increasing abundances of H₂O, Cl and F indicate highly incompatible behavior, whereas CO₂ and reduced carbon species appear to decrease in abundance with increasing differentiation. Ferric-ferrous ratios increase from basalt to andesite and reduce to near zero in the rhyodacite. These values are not distinguishable from those previously reported for similar fractionated glasses from the Galapagos 85°W propagating rift, despite the apparent suppression of oxide precipitation in the 85°W suite.