Chemical zoning in wolframite from San Cristobal,Peru

Fifty wolframite crystals from San Cristobal (Peru) were analysed with the electron microprobe for Fe, Mn, and W. Detailed studies of several samples reveal complex compositional zoning within individual crystals. One sample contains two crystals with contrasting zoning: one crystal has a high-Fe core and an Fe-poor rim, whereas the other has an Fe-poor core and a high-Fe rim. This suggests that these two crystals formed at different moments and that the wolframite composition did not change monotonically with time. The full range of wolframite compositions measured is from 28 to 97 mol% ferberite (FeWO₄). Although a range of 59 mol% was determined for one sample, the average range for all fifty samples is 10 mol%. Samples with average compositions in the range of 84–92 mol% ferberite have relatively small compositional variations, whereas those with average compositions in the range of 61–84 mol% are quite variable. On a vertical longitudinal section of the Main Vein of San Cristobal it appears that the low ferberite values correspond spatially with high tungsten grades. The iron content of the wolframite goes through a minimum across its depositional interval. This may be due to a change in the Fe/Mn ratio of the mineralizing solution with either distance or time.     

Physicochemical study of the hubnerite-ferberite (MnWO4-FeWO4) zonal distribution in wolframite (Mn X Fe(1−X)WO4) deposits

A thermochemical approach to the problem of zonal structure in metallogenetics involving the use of Ellingham diagrams and minimization of free energy (ΔG) agrees closely with the “normal” zonal structure as defined by Fersman (1934). This approach is applied to the hubnerite-ferberite (MnWO₄-FeWO₄) solid solution in order to elucidate the repartition law of the Mn/Fe ratio in wolframite (Mn _X Fe_(1?X)WO₄). The study requires experimental determination of thermodynamical data, such as enthalpy ΔH of the solid solution, which is obtained using a high-temperature calorimetric method developed for this purpose. The calculation leads to an equation which gives the Mn molar value of wolframite with respect to temperature and the Mn/Fe ratio of the mineralizing solution. It is theoretically demonstrated that a high manganese content in wolframite is connected with high deposition temperature, but the decrease of the Mn/Fe ratio is a consequence of the decrease of the Mn/Fe ratio in the mineralizing solution, as can be observed in the Borralha deposit from which the geochemical study has been made. Conversely, a rapid lowering of the temperature of deposition leads to an increase of the Mn/Fe ratio in wolframite. Consequently, this ratio cannot be used as a geologic thermometer, but rather as an indicator of the position of the source of the mineralization.     

South-to-north pyroxenite–peridotite source variation correlated with an OIB-type to arc-type enrichment of magmas from the Payenia backarc of the Andean Southern Volcanic Zone (SVZ)

New high-precision minor element analysis of the most magnesian olivine cores (Fo_85–88) in fifteen high-MgO (Mg#_66–74) alkali basalts or trachybasalts from the Quaternary backarc volcanic province, Payenia, of the Andean Southern Volcanic Zone in Argentina displays a clear north-to-south decrease in Mn/Fe_ol. This is interpreted as the transition from mainly peridotite-derived melts in the north to mainly pyroxenite-derived melts in the south. The peridotite–pyroxenite source variation correlates with a transition of rock compositions from arc-type to OIB-type trace element signatures, where samples from the central part of the province are intermediate. The southernmost rocks have, e.g., relatively low La/Nb, Th/Nb and Th/La ratios as well as high Nb/U, Ce/Pb, Ba/Th and Eu/Eu* = 1.08. The northern samples are characterized by the opposite and have Eu/Eu* down to 0.86. Several incompatible trace element ratios in the rocks correlate with Mn/Fe_ol and also reflect mixing of two geochemically distinct mantle sources. The peridotite melt end-member carries an arc signature that cannot solely be explained by fluid enrichment since these melts have relatively low Eu/Eu*, Ba/Th and high Th/La ratios, which suggest a component of upper continental crust (UCC) in the metasomatizing agent of the northern mantle. However, the addition to the mantle source of crustal materials or varying oxidation state cannot explain the variation in Mn and Mn/Fe of the melts and olivines along Payenia. Instead, the correlation between Mn/Fe_ol and whole-rock (wr) trace element compositions is evidence of two-component mixing of melts derived from peridotite mantle source enriched by slab fluids and UCC melts and a pyroxenite mantle source with an EM1-type trace element signature. Very low Ca/Fe ratios (~1.1) in the olivines of the peridotite melt component and lower calculated partition coefficients for Ca in olivine for these samples are suggested to be caused by higher H₂O contents in the magmas derived from subduction zone enriched mantle. Well-correlated Mn/Fe ratios in the wr and primitive olivines demonstrate that the Mn/Fe_wr of these basalts that only fractionated olivine and chromite reflects the Mn/Fe of the primitive melts and can be used as a proxy for the amount of pyroxenite melt in the magmas. Using Mn/Fe_wr for a large dataset of primitive Payenia rocks, we show that decreasing Mn/Fe_wr is correlated with decreasing Mn and increasing Zn/Mn as expected for pyroxenite melts.     

Geochemistry of cassiterite and wolframite from tin and tungsten quartz veins in Portugal

Cassiterite and wolframite compositions from Sn > W- and W > Sn-bearing quartz veins in Northern and Central Portugal are compared to provide evidence on fluid compositions. In Sn > W-bearing quartz veins, euhedral cassiterite shows sequences of alternating parallel darker and lighter zones. The darker zones are pleochroic, oscillatory zoned, exhibit exsolutions of columbite and ixiolite and are richer in Nb, Ta and Fe than the lighter zones which consist of nearly pure SnO₂. Cassiterite from W > Sn-bearing quartz veins is usually zoned, with homogeneous and slightly pleochroic darker zones, which are chemically similar to lighter zones. Both zones have inclusions of rutile and rare ilmenite. The darker zones of cassiterite from the former veins are richer in Nb, Ta and Fe contents and poorer in Ti than the darker and lighter zones of cassiterite from the latter veins. This is attributed to differences in the composition of magmatic hydrothermal fluids.Wolframite compositions from Sn > W- and W > Sn-bearing quartz veins do not show any significant distinction, because they precipitate from relatively similar magmatic hydrothermal fluids. In some deposits, most wolframite crystals are homogeneous, but others are heterogeneous. Inner patches, rich in a hübnerite component, rarely occur in crystals from the Filharoso and Panasqueira deposits. Zoned crystals, showing an increase in Fe and a decrease in Mn from core to rim, were found in the Vale das Gatas deposit. Complex oscillatory zoned crystals occur. In the Carris deposit, later wolframite contains inclusions of scheelite, partially replaces it and is richer in Fe and poorer in Mn than earlier wolframite. Wolframite from Sn > W-bearing quartz veins in the Argozelo deposit and W > Sn-bearing quartz veins from Vale das Gatas and Panasqueira deposits has significant Nb content. This does not depend on the Fe and Mn content of the wolframite, but W content is negatively correlated with Nb content. Only very rare single crystals of wolframite show an increase in W and a decrease in Nb from core to rim. Sn > W-bearing quartz veins contain wolframite poorer in Nb than the darker zones of cassiterite, which exsolved columbite and ixiolite. In W > Sn-bearing quartz veins from Panasqueira and Vale das Gatas, the wolframite has a higher Nb content than the cassiterite, which contains rutile inclusions enriched in Nb, because cassiterite and wolframite are derived from two distinct magmatic hydrothermal fluids of different age. The fluid responsible for wolframite precipitation will have a similar composition to that resulting from the evolution of the fluid responsible for cassiterite precipitation in the Sn > W-bearing quartz veins.     

天然黑钨矿可见光催化活性的实验研究

天然半导体矿物具有优良的日光催化特性。本研究选取天然钨酸盐作为研究对象,对武鸣、栗木、崇义3个不同矿区的天然黑钨矿进行了矿物学及光催化实验探究。利用X射线衍射、拉曼光谱、红外光谱、电子探针微区分析对天然样品的结构与成分进行分析,鉴定其主要矿物相为黑钨矿(Fe,Mn)[WO4],从武鸣、栗木到崇义矿区,Fe/Mn摩尔分数比从7.1、0.9到0.3依次降低。利用紫外可见漫反射测得武鸣、栗木、崇义地区样品禁带宽度分别为1.5、1.6和1.7eV,说明其具有良好的可见光响应。在pH为7的条件下用质量浓度为1g/L的样品对5mg/L的有机染料亚甲基蓝(MB)进行光催化实验(含0.01mol/L H2O2 ),结果表明武鸣地区黑钨矿实验组降解MB的效果最佳,3h后其效率分别是栗木、崇义地区样品的1.1倍和1.6倍。电子顺磁共振谱检测结果显示,反应过程中均产生氧化性羟自由基(·OH),其中效果最好的武鸣黑钨矿产生的·OH信号更强;不同自由基捕获实验证明·OH在光催化反应过程中起主要作用。进一步选取武鸣黑钨矿开展光催化降解机制研究,实验结果显示:光照下黑钨矿与H2O2共存的实验组对MB的脱色降解率可达99%(3h),只有黑钨矿的对照组降解7%的MB,只有H2O2 的对照组降解31%的MB;黑暗条件下,同时添加黑钨矿与H2O2的对照组对MB的去除率为34%。不同H2O2 浓度条件下黑钨矿降解MB符合准一级动力学方程,说明降解过程与催化剂含量无关,H2O2 更多的是充当电子受体。分析认为,不同产地黑钨矿日光催化效率与矿物铁含量呈正相关,与禁带宽度呈负相关,推测其反应机理是光催化与芬顿反应协同产生的·OH将MB氧化降解。本研究为开发利用天然矿物治理环境污染提出了新方法。     

Geochemistry of ferromanganese nodules from DOMES site a,Northern Equatorial Pacific: Multiple diagenetic metal sources in the deep sea

The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/δ-MnO₂ ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/δ-MnO₂ ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression.All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment.Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form.     

锰结核生长与沉积环境的关系

本文收集了48组世界大洋各种沉积环境锰结核化学组成和生长速率数据并计算了它们的铁锰通量；讨论了不同环境的锰结核的铁锰含量之间的关系，以及锰通量与铁通量、Mn/Fe比的相关性；导出了由锰结核锰铁含量计算生长速率的经验关系；从本质上揭示了锰结核化学组成、生长速率与沉积环境的内在联系，为探讨锰结核形成机理提供了有力的依据。     

Vestoid cosmic spherules from the South Pole Water Well and Transantarctic Mountains (Antarctica): A major and trace element study

We present major and trace element data of five glass cosmic spherules (CS) with differentiated compositions recovered in the South Pole Water Well and the Transantarctic Mountains, Antarctica. The differentiated CS were first identified using Fe/Mg and Fe/Mn ratios and we have now added high Rare Earth Element concentrations (5 < REE_N < 14), and low siderophile element abundances (e.g. Ni = 25 ± 27 ppm) as characteristics. We propose that the siderophile depletions observed in differentiated CS result from the segregation of these elements into the core of their parent body during differentiation. Then, the high Fe/Mg ratios of differentiated CS result from their low MgO contents. Combined with their high level of REE enrichment, this indicates that the precursors formed through basaltic melt extraction from the asteroid/planetary source. As Fe/Mn and Fe/Mg ratios cannot distinguish between a Martian or Vestoid origin, we measured trace elements (zinc, cobalt, and vanadium) whose chemical behavior depends on oxidation state, known to be higher in the Martian than in the Vestoid environment. The compositions of the differentiated CS studied in this work share the characteristics of eucrites for all these indicators, providing further evidence that these differentiated CS are samples of a Vesta-like asteroid. However, their precursors show a considerable diversity in their mineralogy when compared to eucrites, that results in a wider range of major (Ca and Al) and trace element (Ba, Sr, Sc, and V) composition in differentiated CS.     

A theoretical approach to oscillatory zoning affecting wolframite crystals

Oscillatory zoning in (Mn, Fe)WO₄ solid solutions of wolframite consists of a crystalline arrangement of successive Mn-rich and Fe-rich layers. Thermochemical data show that during crystal growth the Mn/Fe ratio in the mineral is greater than in the mineralizing medium. If a diffusion process affects the Mn ion in the solution, a continuous zoning should occur as observed for other solid solutions. The theory developed in this paper emphasises that a continuous zoning cannot appear because the elastic energy needed to adjust two cells with different lattice parameters is greater than the thermodynamic energy required to deposit a cell with the same composition but with a solution of a different Mn/Fe ratio. The reversal of the two energies due to a large depletion in Mn of the solution entails an abrupt change in composition. The relevance of the theory can be checked with the help of a compositional profile found in literature, by calculating with a good approximation the Mn molar value of one layer, if the Mn molar value of the other is known.     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

Implications of elemental concentrations for provenance, redox conditions, and metamorphic studies of shales and limestones near Pueblo, CO, USA

Major element and some trace element compositions (including the REE) of shales, carbonate-rich shales, and limestones of Late Cretaceous age have been analyzed at two outcrops near Pueblo, CO. Elemental ratios that are characteristic of the provenance of terrigenous debris that are the least variable with changing percent acid insoluble residue vs. percent calcite are Th/Cr, La/Co, (La/Lu)_cn, and Eu/Eu*. The Ce/Ce*, La/Sc, and La/Cr ratios, however, are only constant when greater than 30% of a sample is composed of acid insoluble residue. At less than 30% acid insoluble residue, these elemental ratios increase markedly. The Th/Co and Th/Sc ratios are fairly constant from nearly 0% to about 60% acid-insoluble residue. Above 60% residue, these ratios increase due to the high concentration of Th in the Graneros to Hartland shales at Everhart Ranch. The average of the Th/Co, Th/Sc, Th/Cr, La/Co, La/Sc, and La/Cr ratios are similar to those of the MCS (mid-continent shales) and PAAS (Post-Archean Australian shales). Thus, these carbonate-rich to carbonate poor rocks analyzed in this study contain terrigenous debris that has been derived from granitoids similar to those that supplied debris to the MCS and PAAS. The Ce/Ce* ratios are lower and the Mn* (Mn*=log[(Mn_sample/Mn_shales)/(Fe_sample/Fe_shales)]) values are more positive in the more calcite-rich Bridge Creek and Ft. Hays limestones than in the other units, suggesting that they formed in an oxidizing environment. The Ce/Ce* are the highest and the Mn* values are the most negative in the Graneros to Hartland shales, suggesting that they formed under more reducing conditions.The elemental concentration of one sample relative to that of another sample over a few meters distance usually vary in small amounts (e.g., medians of the ratios of the same elements between adjacent samples ranges from 1.06 to 1.70). However, the ratio of elemental concentrations between adjacent samples can sometimes be quite large. The least variation of elemental ratios between adjacent samples often occurs within the more carbonate-poor shales; the greatest variation occurs within the limestones. Thus, trying to decipher local movement of elements due to metamorphism in similar carbonate shale-limestone sequences should be done cautiously since local elemental variation due to sedimentary processes can be large.     

黑钨矿类质同象系列的红外光谱研究

本文是对黑钨矿类质同象系列研究的一个组成部分。测试结果表明在中红外区及远红外区的某些吸收谱带,其频率和强度的变化与黑钨矿中两端员组份FeWO_4和MnWO_4的相对含量有良好的线性相关关系。文中给出了频率变化的相关方程和相关图,并讨论了频率位移和强度变化的内部机制。     

Ferromanganese nodules from the Kara Sea: Interrelation between organic matter and ore elements

This study presents data on Fe–Mn nodules first recovered from the northeastern part of the Kara Sea. Analysis of the geochemical indicators of organic matter and major and trace element compositions of nodules showed that samples with strong Mn enrichment (Mn/Fe = 2.38, on average) are dominated by terrestrial organic matter (OM), whereas Fe-rich samples (Mn/Fe = 0.20, on average) are dominated by marine biogenic OM. The variation in the n-alkane abundances in the studied nodules is independent of the sampling sites and nodule morphology. This study was conducted for the first time in the Artic region.

     

Mineralogical controls on mine drainage of the abandoned Ervedosa tin mine in north-eastern Portugal

The Ervedosa Mine, in north-eastern Portugal, has Sn-bearing quartz veins containing cassiterite and sulphides that cut Silurian schists and a Sn-bearing muscovite granite. These veins were mined for Sn and As₂O₃ until 1969. Cassiterite, the main Sn ore, has alternate lighter and darker growth-zones. The darker zones are richer in Fe, Nb, Ta and Ti, but poorer in Sn than the adjoining lighter zones. Exsolution blebs of ferrocolumbite, manganocolumbite, Ti ixiolite, rutile, ilmenite and rare wolframite were found in the darker zones. Arsenopyrite is the most abundant sulphide and contains inclusions of pyrrhotite, bismuth, bismuthinite and matildite. Other sulphides are pyrite, sphalerite, chalcopyrite and stannite. Secondary solid phases consisting mainly of hydrate sulphate complexes of Al, Fe, Ca and Mg (aluminocopiapite, copiapite, halotrichite, pickeringite, gypsum and alunogen, meta-alunogen) occur at the surface of the Sn-bearing quartz veins and their wall rocks (granite and schist), while oxides, hydroxides, arsenates and residual mineral phases (albite, muscovite and quartz) occur in mining tailings. Toxic acid mine waters (acid mine drainage AMD), which have high conductivity and significant concentrations of As, SO₄ and metal (Cu, Zn, Pb, Fe, Mn, Cd, Ni and Co), occur in an area directly affected by the mine. Surface stream waters outside this area have low conductivity and a pH that is almost neutral. Metal and As concentrations are also lower. Stream waters within the impact area have an intermediate composition, falling between that of the AMD and the natural stream waters outside impact area. Waters associated directly with mineralised veins must not be used for human consumption or agriculture.     

Intercrystalline cation partitioning between minerals of the triplite-zwieselite-magniotriplite and the triphylite-lithiophilite series in granitic pegmatites

Minerals of the triphylite-lithiophilite, Li(Fe, Mn)PO₄, and the triplite-zwieselite-magniotriplite series, (Mn, Fe, Mg)₂PO₄F, occur in the late stage period of pegmatite evolution. Unfortunately, neither are the genetic relationships between these phosphates fully understood nor are thermodynamic data known. Consequently, phosphate associations and assemblages from 8 granitic pegmatites — Clementine II, Rubicon II and III, and Tsaobismund (Namibia); Hagendorf-Süd and Rabenstein (Germany); Valmy (France); Viitaniemi (Finland) — have been tested for compositional zoning and intercrystalline partitioning of main elements by electron microprobe techniques. Although the selected pegmatites display varying degrees of fractionation, and the intergrowth textures indicate different genetic relationships between the phosphates, the plots of mole fractions X _Fe=Fe/(Fe+Mn+Mg+Ca), X _Mn=Mn/(Fe+Mn+Mg+Ca), and X _Mg=Mg/(Fe+Mn+Mg+Ca) can be fitted relatively well with smooth curves in Roozeboom diagrams. Their deviations from symmetrical distribution curves are mainly dependent upon X _Mg or X _Ca, and upon non-ideal solutions. Surprisingly small differences between the partition coefficients were detected for intergrowths of different origin. However, the partitioning of shared components among coexisting phases is clearly dependent upon the conditions of formation. Compositional zoning is observed only when both Fe–Mn phosphates are intergrown mutually or with other Fe–Mn–Mg mineral solid-solutios. Thus, the zoning does not seem to be due to continuous crystallization, but to later diffusion processes. The triplite structure has preference for Mn, Mg, and Ca, while Fe prefers minerals of the triphylite series. A quantification of main element fractionation between minerals of the triphylite and the triplite series is possible in the cases where diffusion can be excluded. For the Fe/(Fe+Mn) ratios of core compositions an equation with a high correlation coefficient (R=0.988) was determined: Fe/(Fe+Mn)_Tr=[Fe/(Fe+Mn)_Li]/{2.737-(1.737)[Fe/(Fe+Mn)_Li]} (Tr=triplite series, Li=triphylite series). Consequently, the Fe/(Fe+Mn) ratio of the triplite series can now also be used in the interpretation of pegmatite evolution, just like that of the triphylite series which has been successfully applied in the past.     

Volatile (Cl,F and S) and major element constraints on subduction-related mantle metasomatism along the alkaline basaltic backarc,Payenia, Argentina

We present data on volatile (S, F and Cl) and major element contents in olivine-hosted melt inclusions (MIs) from alkaline basaltic tephras along the Quaternary Payenia backarc volcanic province (~34°S–38°S) of the Andean Southern Volcanic Zone (SVZ). The composition of Cr-spinel inclusions and host olivines in Payenia are also included to constrain any variations in oxygen fugacity. The variation of potassium, fluorine and chlorine in MIs in Payenia can be modelled by partial melting (1–10%) of a variously metasomatised mantle. The high chlorine contents in MIs (up to 3200 ppm) from Northern Payenia require addition of subduction-related fluids to a mantle wedge, whereas volatile signatures in the southern Payenia are consistent with derivation from an enriched OIB source. Cl and Cl/K ratios define positive correlations with host olivine fosterite content (Fo_80-90) that cannot be explained by olivine fractionation, degassing and/or degree of mantle melting. Neither can the correlation between SiO₂ and TiO₂ in the MIs and host olivine Fo-content be explained by magmatic differentiation processes. Instead these correlations essentially require a south to north mantle source transition from a low Mg# pyroxenite (from recycled eclogite) to a high Mg# fluid metasomatised peridotite. The Cl/K and S/K ratios in Payenia MIs extend from enriched OIB-like signatures (south) to Andean SVZ arc like signatures (north). We show that the northward increase in S, Cl and S/K is coupled to a northward increase in melt oxidation states and thus in Fe³⁺/Fe^tot ratios in the magmas. The increase in oxidation state also correlates with an increase of Mn/Fe (olivine) ratios. We calculate that 25% of the apparent north–south pyroxenite–peridotite source variation in Payenia (based on olivine Mn/Fe ratios) can be explained by the south to north variation in melt oxidation states.     

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

Geochemistry of waters associated with the old mine workings at Fonte Santa (NE of Portugal)

The quartz veins containing scheelite from Fonte Santa mine cut the Lower Ordovician quartzites. A muscovite–biotite granite (G1) and a muscovite granite (G2), both S-type, crop out close to the Fonte Santa mine and are related to the Moncorvo–Bemposta shear zone. The most altered samples of G2 show intense muscovitization and microclinization and contain chlorite, columbite–tantalite, wolframite, W-ixiolite and Fe-oxides. The tin-bearing granites contain 18 ppm (G1) and 73 ppm (G2) Sn. The most altered samples of G2 correspond to a tungsten granite. The quartz veins contain muscovite, chlorite, tourmaline, scheelite, pyrrhotite, pyrite, sphalerite, chalcopyrite, galena, arsenopyrite, iron oxides, Fe sulfates, phosphates of Pb, Fe and Al. The Fonte Santa mine area was exploited for W between 1942 and 1982. At the end of November 2006, a flood event damaged the tailings dam of Fonte Santa mine, releasing contaminated material and increasing contaminant levels in water within the area of influence of the mine. The waters related to the Fonte Santa mine are poorly mineralized, with electrical conductivity of < 965 µS/cm, and of a mixed type or HCO₃⁻ and SO₄²⁻ types. Most pH values (5.0−8.5) indicate that there is no significant acidic drainage in the region, as found in other areas. More acidic values (pH = 3.4) were found in the mine's lagoon. Waters associated with mineralized veins and old mine activities have Fe and Mn concentrations that forbid their use for human consumption and agriculture. Natural Na, Mg and K water contents are associated with the alteration of albite, chlorite and muscovite of country rock, while Ca with the W-bearing quartz veins. Weathering agents are carbonic and sulphuric acids and the latter has a strong influence in areas draining fine-grained mine tailings.     

黑钨矿中锰铁比值的成因意义研究

在地质找矿勘探工作中,研究黑钨矿的锰铁比值可以帮助确定矿床的成因类型,并且,在某种程度上还可以当作相对的“地质矿物温度计”来应用。在自然界,影响黑钨矿中锰铁比值的因素甚多,诸如,成矿介质的pH值和Eh值、化学反应动力状况、区域地球化学特点、压力以及形成温度等。关于成矿温度,在许多情况下虽然不是影响黑钨矿中锰铁比值的决定性因素,但仍不失为一重要因素,故其与黑钨矿中锰、铁成分变化的关系引起了国内外许多研究者的重视。     

Iron/manganese ratio and manganese content in shield lavas from Ko’olau Volcano, Hawai’i

Precise Fe/Mn ratios and MnO contents have been determined for basalts from the Hawaiian shields of Ko’olau and Kilauea by inductively coupled plasma mass spectrometry. It is well known that the youngest Ko’olau (Makapu’u-stage) shield lavas define a geochemical endmember for Hawaiian lavas in terms of CaO and SiO₂ contents and isotopic ratios of O, Sr, Nd, Hf, Pb, and Os. We find that their MnO content is also distinct. Despite the small range in MnO, 0.146 to 0.176 wt%, the precision of our data is sufficient to show that among unaltered Ko’olau lavas MnO content is correlated with Nd-Hf-Pb isotopic ratios, La/Nb and Al₂O₃/CaO elemental ratios, and contents of SiO₂, MgO and Na₂O + K₂O adjusted for olivine fractionation. These trends are consistent with two-component mixing; one endmember is a SiO₂-rich, MnO-, and MgO-poor dacite or andesite melt, generated by low degree (10-20%) partial melting of eclogite. Since this low-MgO endmember (dacite or andesite melt) has very low FeO and MnO contents, mixing of high Fe/Mn dacite or andesite melt with a MgO-rich picritic melt, the other endmember, does not significantly increase the Fe/Mn in mixed magmas; consequently, Ko’olau and Kilauea lavas have similar Fe/Mn. We conclude that the high Fe/Mn in Hawaiian lavas relative to mid-ocean ridge basalt originates from the high MgO endmember in Hawaiian lavas.