Distribution of Ni,Ga, Ge and Ir between metal and silicate portions of H-group chondrites

Concentrations of Ni, Ga, Ge and Ir have been determined in the metal and silicate portions of 21 chondrites, including 15 H chondrites. The H-group metal shows the following concentration ranges: 7.2–9.4 per cent Ni, 2.4–18 ppm Ga, 61–70 ppm Ge and 1.6–4.6 ppm Ir, and concentrations in H-group silicates are 94–380 ppm Ni, 3.0–9.2 ppm Ga, 0.06–0.66 ppm Ge and 0.03–0.12 ppm Ir. The Ni, Ge and Ir contents in the metal are positively correlated with each other and with the Fe content of olivine, as expected from oxidation-reduction or combined metal-silicate-fractionation/oxidation-reduction models. Metal/silicate concentration ratios for Ir are lower than for Ge and Ni, despite the fact that Ir is more easily reduced to the elemental form. This may indicate that at the formation location of the H-group chondrites in the solar nebula, substantial amounts of Ir were present in condensed form at temperatures which were so high that Fe and Ni were present mainly as vapor. The metal/silicate concentration ratios of Ga and Ge are lower in type-3 ordinary chondrites than in types 4–6. Apparently appreciable fractions of these elements condensed from the nebula in oxidized form and entered the metal during later thermal events. That Ga and Ge were redistributed during recrystallization, whereas appreciable Ir remained in the silicate fraction, probably indicates that Ir faced a substantially greater diffusional barrier than did Ga and Ge.     

Mesosiderites—I. Compositions of their metallic portions and possible relationship to other metal-rich meteorite groups

The metal from 17 mesosiderites has been analyzed for Ni, Ga, Ge and Ir by the techniques of atomic-absorption spectrometry and neutron activation. Most mesosiderite metal samples fall in a narrow compositional range: Ni, 7·0–9·0 per cent; Ga, 13–16 ppm; Ge, 47–58 ppm; and Ir, 2·4–4·4 ppm. Most of those falling outside these ranges belong to Powell's (1971) least-metamorphosed type. Mesosiderite metal falls in the same general composition range as IIIAB irons, IIIE irons, pallasites and H-group chondrite metal. There are distinct differences in detail, however, and firm evidence for a close genetic relationship between any of these groups and the mesosiderites is lacking. Metallic portions of Weekeroo-type irons tend to have slightly higher Ni, Ga, Ge and Ir contents than found in mesosiderite metal, and the two groups tend to form a single trend on all plots. The Weekeroo-type silicates closely resemble mesosiderites in terms of orthopyroxene composition and oxygen-isotope ratio. We interpret these similarities to indicate that the silicate and metallic portions of these two groups are closely related; if the mesosiderite silicates and metal were initially formed in separate parent bodies, these were of similar composition and formed at about the same distance from the Sun.     

Formation of metal in Grosvenor Mountains 95551 and comparison to ordinary chondrites

Siderophile element abundances in individual metal grains in the ungrouped chondrite Grosvenor Mountains (GRO) 95551 and in the ordinary chondrites Tieschitz H3.6, Soko-Banja LL4, and Allegan H5 were measured with laser ablation-inductively coupled plasma mass spectrometry. Matrix metal in GRO 95551 falls into two distinct compositional groups, a high-Ni group with 7.2 ± 0.4 wt% Ni and a low-Ni group with 3.7 ± 0.1 wt% Ni, indicating that kamacite/taenite equilibration at ∼1020 K was followed by rapid cooling. The nonrefractory siderophile elements P, Co, Cu, Ga, Ge, As, Pd, and Au also partition between the high-Ni and low-Ni metal in a manner consistent with kamacite/taenite fractionation, but the refractory siderophiles Ru, Re, Os, Ir, and Pt show correlated variations that are unrelated to kamacite/taenite partitioning and indicate that variations in refractory components of the metal were not completely erased during equilibration at ∼1020 K. The Ni-normalized bulk metal composition of GRO 95551 is refractory depleted and volatile rich relative to Bencubbin and related metal-rich chondrites but bears strong similarities to equilibrated ordinary chondrite metal. GRO 95551 represents a new chondrite type with chemical affinity to the ordinary chondrites. Individual metal grains in unequlibrated ordinary chondrites also have correlated variations in refractory siderophile contents that cannot be produced by redox processes alone; these variations span three orders of magnitude and diminish with increasing metamorphic grade of the ordinary chondrites.     

Composition of the metal phases in ordinary chondrites: implications regarding classification and metamorphism

EMP determinations of Fe, Co and Ni in the metal phases of ordinary chondrites confirm the report of Sears and Axon that kamacite Co contents show restricted, nonoverlapping ranges in the three groups; ranges are 3.3–4.8 mg/g in H, 6.7–8.2 mg/g in L and 15–110 mg/g in LL. Experimental data by Widge and Goldstein show that the Ni concentration of the $\text{α}\text{(α + γ)}$ boundary increases with increasing Co concentration: unexpectedly, we find lower kamacite Ni concentrations in unequilibrated LL chondrites (44–55 mg/g) than in H and L chondrites (57–69 mg/g). We infer that, at temperatures below 550° C increasing Co causes a decrease in the equilibrium kamacite Ni concentration of an α-γ system. Although some evidence indicates that the equilibrated L chondrites Barratta, Knyahinya and Shaw have siderophile concentrations lower than the normal L-group range, they have kamacite and taenite Co concentrations in the L-group range.Metal-phase studies of petrologic type-3 ordinary chondrites having highly unequilibrated silicates showed a wide range in the degree of matrix kamacite equilibration ranging from nearly equilibrated in Mezö-Madaras to highly unequilibrated in Bishunpur, Ngawi and Semarkona. Kamacite in chondrule interiors is highly unequilibrated in all 9 chondrites, and in each setting taenite data are consistent with the expectation that it should be less equilibrated than kamacite. Our kamacite Co data confirm that Sharps is H and Hallingeberg. Khohar and Mezö-Madaras are L chondrites. Chainpur and Parnallee have kamacite Co concentrations between the L and LL ranges: we present evidence indicating that they are truly intermediate, i.e. neither L nor LL. Highly unequilibrated Ngawi is either LL or, less likely, still more oxidized. Bishunpur and Semarkona have mean kamacite Co concentrations in the H range but too unequilibrated to be used for classification. The highly heterogeneous compositions of the metal in Bishunpur, Ngawi and Semarkona indicate that their metal partially preserves properties established during nebular processes. Most of the taenite in these chondrites has high Ni contents (>470 mg/g) and is essentially unzoned; much of the kamacite is polycrystalline with crystals ?5μm across. Metamorphism causes tiny grains to disappear, increases the grain size of both kamacite and taenite, tends to equilibrate metallic minerals and, during cooling, can produce zoned taenite.A petrologic type-5 clast in the Ngawi LL3 chondrite has 3 coexisting metal phases, clear taenite (540 mg/g Ni, 21 mg/g Co), kamacite (30 mg/g Ni, 120 mg/g Co) and a phase tentatively identified as ordered FeCo (8.5 mg/g Ni, 370 mg/g Co).     

Bulk compositions of metallic Fe-Ni of chondrites： Constraints on fractionation of siderophile and chalcophile elements

Bulk compositions of metallic Fe-Ni from two equilibrated ordinary chondrites, Jilin (H5) and Anlong (H5), and two unequilibrated ones, GRV 9919 (L3) and GRV 021603 (H3), were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The CI-, Co-normalized abundances of siderophile and chalcophile elements of metallic Fe-Ni from the unequilibrated ordinary chondrites correlate with 50% condensation temperatures (i.e., volatility) of the elements. The refractory siderophile elements (i.e., platinum group elements, Re), Au, Ni and Co show a flat pattern (1.01×CI Co-normalized), while moderate elements (As, Cu, Ag, Ga, Ge, Zn) decrease with volatility from 0.63×CI (Co-normalized, As) to 0.05×CI (Co-normalized, Zn). Cr and Mn show deficit relative to the trend, probably due to their main partition in silicates and sulfides (nonmagnetic). Metallic Fe-Ni from the equilibrated ordinary chondrites shows similar patterns, except for strong deficit of Cr, Mn, Ag and Zn. It is indicated that these elements were almost all partitioned into silicates and/or sulfides during thermal metamorphism. The similar deficit of Cr, Mn, Ag and Zn was also found in iron meteorites. Our analyses demonstrate similar behaviors of W and Mo as refractory siderophile elements during condensation of the solar nebula, except for slight depletion of Mo in the L3 and H5 chondrites. The Mo-depletion of metallic Fe-Ni from GRV 9919 (L3) relative to GRV 021603 (H3) could be due to a more oxidizing condition of the former than the latter in the solar nebula. In contrast, the Mo-depletion of the metallic Fe-Ni from the H5 chondrites may reflect partition of Mo from metal to silicates and/or sulfides during thermal metamorphism in the asteroidal body.     

Distribution of tungsten and molybdenum between metal,silicate, and sulphide phases of meteorites

The concentrations of W, Mo, Co and Ni have been determined by neutron activation analysis in the separated metal, silicate and troilite of twelve chondrites—nine ordinary, two enstatite and one carbonaceous. Concentration ratios of W and Mo in silicate relative to metal are 0.03–0.6 and 0.05–0.55, respectively, and those of W in the troilite relative to the metal are 0.01–0.2. The contents of Mo in the troilite are nearly equal to those in the metal. Co and Ni are more depleted than W and Mo both in the silicate and troilite.Thermodynamic considerations have been made for determined concentration ratios. In some L-chondrites, W is depleted in the silicate by a factor of three to four of the value estimated from the correlation line between H- and LL-chondrites. This tendency seems to suggest a relatively higher temperature in the thermal history of these L-chondrites.     

Abundance patterns of thirteen trace elements in primitive carbonaceous and unequilibrated ordinary chondrites

A neutron activation analysis technique was used to determine Au, Re, Co, Mo, As, Sb, Ga, Se, Te, Hg, Zn, Bi and Tl in 11 carbonaceous chondrites, 12 unequilibrated ordinary chondrites (UOC), and 4 equilibrated ordinary chondrites. The first 6 elements are ‘undepleted’, the next 3 ‘normally-depleted’ and the last 4 ‘strongly-depleted’. Except for Hg, ‘depleted-element’ abundances in carbonaceous chondrites lead to mean relative ratios of C1:C2:C3 = 1.00:0.53:0.29, i.e. those predicted by a two-component (mixing of high-temperature and low-temperature fractions) model. The last 4 nominally ‘undepleted’ elements are somewhat depleted in ordinary chondrites, As and Sb showing partial depletion in C3 and the latter in C2 chondrites as well. This requires a modification of the two-component model to indicate that deposition of elements during condensation of high temperature material was not an all-or-nothing process.Apart from Bi and Tl, the elements studied have similar abundances in unequilibrated and equilibrated ordinary chondrites and only the former are unquestionably correlated with the degree of disequilibrium in silicate minerals. Only some ‘strongly-depleted’ elements exhibit at least one of the following—proportional depletion in UOC, progressive depletion in petrographic grades 3–6 ordinary chondrites and enrichment in the gas-containing dark portion of gas-rich, light-dark meteorites—indicating that such depletion does not ensure that an element will exhibit these trends. Partly or completely siderophile As, Au, Co, Ga, Mo, Re and Sb vary with chemical type in the same manner in both unequilibrated and equilibrated ordinary chondrites and doubtless reflect a process involving fractionation of metallic iron.     

Trace elements in primitive meteorites—VI. Abundance patterns of thirteen trace elements and interelement relationships in unequilibrated ordinary chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 13 different unequilibrated ordinary chondrites (UOC), i.e. those having chemicallyinhomogeneous silicates. This study together with prior data completes our coverage of this group of 23 primitive chondrites. Four elements are quite variable in UOC (Cd—20 x, In—30 x, Bi—300 x and Tl—1300 x), the others varying by 2–8 x. Three highly-depleted elements—Bi, In and Tl—are richer by 5–35 x in unequilibrated chondrites than in their equilibrated congeners. All 3 elements vary directly in characteristic fashion with disequilibrium parameters for olivine and pyroxene in UOC and generally with petrologic type 3 > 4 > 5 > 6. The data do not provide unambiguous evidence for nebular fractionation of siderophile elements. Examination of statistically-significant interelement relationships among various ordinary chondrite populations involving 34 elements reveals patterns distinct from those of other chondritic groups. These patterns reflect nebular metal-silicate fractionation which preceded or accompanied thermal fractionation. The results point to significant differences in the formation of primitive carbonaceous, enstatite and ordinary chondrites.     

Chemical and physical studies of type 3 chondrites—VI: Siderophile elements in ordinary chondrites

The abundances of Fe, Ni, Co, Au, Ir, Ga, As and Mg have been determined by instrumental neutron activation analysis in 38 type 3 ordinary chondrites (10 of which may be paired) and 15 equilibrated chondrites. Classification of type 3 ordinary chondrites into the H, L and LL classes using oxygen isotopes and parameters which reflect oxidation state (Fa and Fs in the olivine and pyroxene and Co in kamacite) is difficult or impossible. Bulk compositional parameters, based on the equilibrated chondrites, have therefore been used to classify the type 3 chondrites. The distribution of the type 3 ordinary chondrites over the classes is very different from that of the equilibrated chondrites, the LL chondrites being more heavily represented. The type 3 ordinary chondrites contain 5 to 15 percent lower abundances of siderophile elements and a compilation of the present data and literature data indicates a small, systematic decrease in siderophile element concentration with decreasing petrologic type. The type 3 ordinary chondrites have, like the equilibrated ordinary chondrites, suffered a fractionation of their siderophile elements, but the loss of Ni in comparison with Au and Ir is greater for the type 3 chondrites. These siderophile element trends were established at the nebula phase of chondritic history and the co-variation with petrologic type implies onion-shell structures for the ordinary chondrite parent bodies. It is also clear that the relationship between the type 3 and the equilibrated ordinary chondrites involves more than simple, closed-system metamorphism.     

Silicate inclusions in group IAB irons and a relation to the anomalous stones Winona and Mt Morris (Wis)

Silicates are found in many group IAB irons; in some cases as abundant angular cm-sized inclusions and in other cases as smaller fragments or single grains in troilite or graphite nodules. The mineralogy of the silicates is chondritic—olivine, pyroxene, albitic plagioclase—as is the bulk composition. The degree of oxidation of the olivine and pyroxene is intermediate between E and H chondrites (Fa 1–8, Fs 4–9). IAB inclusions have ages of about 4.5 Gyr, I¹²⁹-Xe¹²⁹ formation intervals in the ranges of chondrites and contain planetary-type rare gases.Samples of San Cristobal, Campo del Cielo, Mundrabilla and Woodbine were examined by microprobe and bulk inclusions from Campo del Cielo, Copiapo, Landes and Woodbine were analyzed by instrumental and radiochemical neutron activation analysis. Nonvolatile lithophilic and siderophih'c elements in Copiapo, Landes and Woodbine have approximately chondritic abundances. The chondritic level of lithophiles indicates the inclusions have not undergone igneous differentiation while the chondritic levels of siderophiles is evidence the metal is native to the inclusions and not matrix metal injected into the silicates. The two Campo del Cielo inclusions analyzed have roughly chondritic abundances of lithophiles but have fractionated rare earth patterns and widely varying amounts and abundances (relative to Ni) of siderophiles. These inclusions appear to have experienced some partial melting. Siderophile ratios for the inclusions have some differences when compared to matrix metal. One Campo del Cielo inclusion contains kamacite (5.5% Ni) with over 1000 μg Ge.Three-isotope O analyses by Clayton and coworkers of parts of the same or neighboring inclusions to those analyzed chemically place the inclusions slightly below the terrestrial fractionation line of clayton et al. (1976) and rule out the possibility of the inclusions being trapped fragments of one of the ordinary chondrite groups.The IAB silicates formed probably in a similar manner as chondrite groups but in a different region of the nebula and they record the O₂ fugacity and O isotopic composition of that location. They later became trapped in the metal-rich matrix probably as the result of collisions producing the breccialike texture. The relationship of the silicates to the kamacite-taenite structure of the metal requires that the metal-silicate mix have been heated to over 1000 K for an extended period.Two anomalous stony meteorites, Winona and Mt. Morris (Wis), are similar to IAB inclusions in mineralogy, bulk composition, $\text{FeO}\text{(FeO + Mg)}$ ratio of the silicates, and chromite composition and are possibly related to the IAB silicates. Winona also has an age of 4.6 Gyr and contains planetary-type rare gases. Microprobe data are reported for the major minerals of these anomalous meteorites. Although attempts to detect IAB levels of Ge in the metal phases were not successful, the weight of the evidence favors a relationship between these meteorites and IAB     

I-Xe dating of silicate and troilite from IAB iron meteorites

The IAB iron meteorites may be related to the chondrites: siderophile elements in the metal matrix have chondritic abundances, and the abundant silicate inclusions are chondritic both in mineralogy and in chemical composition. Silicate and troilite (FeS) from IAB irons were analyzed by the I-Xe technique. Four IAB silicate samples gave well-defined I-Xe ages [in millions of years relative to Bjurböle; the monitor error (± 2.5 Myr) is not included]: ?3.7 ± 0.3 for Woodbine, ?0.7 ± 0. 6 for Mundrabilla, +1.4 ± 0.7 for Copiapo, and +2.6 ± 0.6 for Landes. The (¹²⁹Xe/¹³²Xe)_trapped ratios are consistent with previous values for chondrites, with the exception of Landes which has an extraordinary trapped ratio of 3.5 ± 0.2. Both analyses of silicate from Pitts gave anomalous I-Xe patterns.Troilite samples were also analyzed: Pitts troilite gave a complex I-Xe pattern, which suggests an age of +17 Myr; Mundrabilla troilite defined a good I-Xe correlation, which after correction for neutron capture on ¹²⁸Te gave an age of ?10.8 ± 0.7 Myr. Thus, surprisingly, low-melting troilite substantially predates high-melting silicate in Mundrabilla.Abundances of Ga, Ge, and Ni in metal from these meteorites are correlated with I-Xe ages of the silicate; meteorites with older silicates have greater Ni contents. No model easily accounts for this result as well as other properties of IAB irons; nevertheless, these results, taken at face value, overall favor a nebular formation model (e.g. Wasson, 1970, Icarus 12, 407–423). The great age of troilite from Mundrabilla suggests that this troilite formed in a different nebular region from the silicate and metal, and was later mechanically mixed with these other phases.The correlation between the trace elements in the metal and the I-Xe ages of the silicate provides one of the first known instances in which another well-defined meteoritic property correlates with I-Xe ages. In addition, almost all the ¹²⁹Xe in Mundrabilla silicate (etched in acid) was correlated with ¹²⁸Xe. These two results further support the validity of the I-Xe dating method.     

The Kelly chondrite: A parent body surface metabreccia

The Kelly brecciated chondrite, originally classified as a polymict breccia, is actually a monomict breccia, based on conclusions from this study. Microprobe analyses of differently textured clasts are very similar to each other and also to well-known LL-type chondrites. Clast and matrix olivine compositions range between Fa_27–31, well within the range of LL-chondrite olivine. A correlation was found between the degree of recrystallization and plagioclase composition; least recrystallized plagioclase is more Ca-rich than fully recrystallized plagioclase. Petrographic observations of shocked, annealed, and unshocked clasts coupled with particle size distribution measurements strongly indicate that Kelly is similar to lunar metabreccias in mode of formation, i.e., repeated mixing and accumulation of disaggregated surface rocks and impacting debris followed by partial annealing under moderate temperatures. At least three breccia generations are indicated. We propose that Kelly is an LL-chondrite parent body metabreccia that represents the final accumulation phase of the parent body. Only LL-type fragments were found in Kelly, which suggests that the parent body consisted of only LL-chondrites and was not a multi-shelled body of H-, L-, and LL-chondrites.     

Comparative stable isotope geochemistry of Ni, Cu, Zn, and Fe in chondrites and iron meteorites

High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes.The observed variations of the ⁶²Ni/⁵⁸Ni, ⁶¹Ni/⁵⁸Ni, and ⁶⁰Ni/⁵⁸Ni ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no ⁶⁰Ni anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45‰ per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation.     

Nitrogen in chondritic metal

We report new nitrogen isotopic data in metals of H-, L- and one LL -chondrites, with N abundances in the range of ∼0.3 to 3.3 ppm and half of these <1 ppm. Nitrogen isotopic signatures in metals with low indigenous N concentrations are modified by cosmic ray spallation components; corrections are required to determine the indigenous N signatures. The metals of type 4 and 5 show uniform indigenous nitrogen (δ¹⁵N = −6.8 ± 0.5 ‰) and confirm a reported possible genetic association of chondritic metal with metal in IIE and IVA iron meteorites. Distinct isotopic signatures are observed in two metal samples of the Portales Valley (H6) meteorite which both are inconsistent with signatures in H4 and H5 chondrites, but possibly reveal a record of impact-induced melting and metamorphism on the parent asteroid. Anomalous nitrogen signatures in metals of type 3 chondrites, on the other hand, may reflect residues of surviving presolar isotopic signatures.     

Restudy of pyroxene-pyroxene equilibration temperatures for ordinary chrondrite meteorites

Electron microprobe analyses of orthopyroxene and Ca-clinopyroxene in 21 ordinary petrographic type 6 chondrites (7 H-, 8 L-, and 6 LL-group chondrites) result in differentK _D (distribution coefficient) values for H-, L-, and LL-group chondrites, which suggest different equilibration temperatures for each group. If we consider the Blander model (Blander 1972), the differences in Fe-Mg distributions for these groups reflect only their different Wo (CaSiO₃) contents, and are not due to differences in equalibration temperature. Ca-clinopyroxene and orthopyroxene in contact with each other give a lower analytical spread and more meaningful results than those analyzed at random. Olivine and orthopyroxene in nearly all analyzed chondrites are homogenous within and between grains; Ca-clinopyroxene shows heterogenous compositions in petrographic types 4 and 5, but is homogenous in type 6. Ca-clinopyroxene in disequilibrated chondrites contains unusual amounts of minor elements Al, Ti, and Cr, a feature that can be used to denote meteorites of this type. Equilibration temperatures for ordinary chondrites, based on the pyroxene-pyroxene geothermometer are not known, although a range of 750–950° C appears to be a fair estimate. The exact equilibration temperatures can be determined only after this geothermometer is carefully calibrated experimentally or empirically, with due consideration given to Wo content.     

Si in the core? New high-pressure and high-temperature experimental data

High-pressure high-temperature experiments have been carried out up to 25 GPa and 2200°C in a multianvil press on assemblages made of silicates and iron-silicon alloys. At 20 GPa, silicon is extracted from the metal phase, forming stishovite reaction rims around metal grains. The silicon content in metal has been measured by analytical electron microscopy and electron microprobe. In contrast with earlier experiments, the present data were obtained by using silicon-rich metal alloys as starting materials instead of studying incorporation of silicon in initially silicon-free metal. As in most of previous studies carried out below 25 GPa, the silicon content in liquid metal increases with increasing pressure and with decreasing oxygen fugacity. The oxygen fugacity in most experiments was calculated by using two independent buffers: iron/?stite (IW) and SiO₂/Si, allowing to link consistently the Fe contents in silicates, the Si contents in metal and the temperatures of the experiments. At oxygen fugacities 4 log units below IW, silicates are in equilibrium with Si-rich metallic alloys (up to 17 wt% of Si in metal at 20 GPa and 2200°C). Extrapolation to 2 log units below IW leads to less than 0.1 wt% Si in the metal phase. Presence of several wt% of silicon in the Earth’s core thus requires highly reduced initial materials that, if equilibrated at conditions relevant to small planets, should already contain significant amount of silicon dissolved in metal.     

Metal and associated phases in Bishunpur,a highly unequilibrated ordinary chondrite

It appears that the highly unequilibrated Bishunpur ordinary chondrite preserves phase relations acquired during solar nebular processes to a relatively high degree; metamorphic temperatures may not have exceeded 300–350°C. The major categories of metal are: 3 kinds of metal in the metal matrix, three kinds in chondrule interiors and 2 kinds in chondrule rims. The fine-grained matrix metal is highly variable in composition: the kamacite Co content (7.8 ± 2.0 mg/g) is within the L-group range (6.7–8.2 mg/g) but extends well above and below; its Ni content (38 ± 5 mg/g) is considerably lower than in more equilibrated chondrites and taenite is Ni-rich ( > 450 mg/g) and unzoned. These compositions imply equilibration at very low temperatures of about 300–350°C. It seems unlikely that volume diffusion could account for the observed relatively unzoned phases; a better model involves mass transport by grain boundary diffusion and grain growth at the indicated temperatures. We find no evidence that the matrix was ever at higher temperatures. Large (50–650 μm) polycrystalline metal aggregates consisting of individually zoned crystals are also found in the matrix; they probably represent clusters formed in the solar nebula. A few large (50–250 μm) round monocrystalline grains are also present in the matrix.Metal-bearing chondrules tend to be highly reduced; they contain low-Ni metal that occasionally contains Si and/or Cr. Silicates in these chondrules tend to have low $\text{FeO}\text{(FeO + MgO)}$ ratios. The Si-rich metal grains are never in contact with silicates and are always surrounded by troilite with a poorly characterized Ca, Cr-sulfide at the metal-troilite interface; they appear to be high temperature nebular condensates that avoided oxidation even during the chondrule forming process. Silicon contents drop below our detection limit when the sulfide coating is absent. Much more common in chondrule interiors are Si-free spheroidal metal grains not associated with sulfides. These have Ni and Co contents very similar to the Si-bearing grains, and appear to be oxidized variants of the same material. The third class of chondrule metal is fine ( ~1 μm) dusty grains inside individual olivine grains. These seem to reflect high temperature in situ reduction of FeO from the olivine.The composition of kamacite is different in sulfide-rich and sulfide-poor chondrule rims and in both cases it is dissimilar to the compositions in the chondrule interiors and matrix; this indicates that chondrule rims could not have resulted from reactions with the matrix, but are primary features acquired prior to accretton.     

Chemical classification of iron meteorites—VIII. Groups IC. IIE,IIIF and 97 other irons

Concentrations of Ni, Ga, Ge and Ir in 106 iron meteorites are reported. Three new groups are defined: IC, IIE and IIIF containing 10, 12 and 5 members, respectively, raising the number of independent groups to 12. Group IC is a cohenite-rich group distantly related to IA. Group IIE consists of those irons previously designated Weekeroo Station type and five others having similar compositions though diverse structures. The IIE irons are compositionally similar to the mesosiderites and pallasites, and the three groups probably formed at similar heliocentric distances. The mixing of the globular IIE silicates with the metal probably occurred during shock events. Group IIIF is a well-defined group of low-Ni and low-Ge irons. The compositions of these groups are summarized as follows:

     

19.

Distribution of indium in ores of some base metal and tin–sulfide deposits in Siberia and the Russian Far East     

I. V. Gaskov  A. G. Vladimirov  A. I. Khanchuk  G. A. Pavlova  V. I. Gvozdev 《Geology of Ore Deposits》2017,59(1):56-67

The study of base-metal massive sulfide and tin–sulfide deposits in Siberia and the Russian Far East has revealed that the indium content in ores exceeding the average statistical value at similar deposits worldwide could be economically important. Sphalerite and chalcopyrite and chalcopyrite, bornite, and sphalerite are the major indium carriers in the base-metal massive sulfide and tin–sulfide ores, respectively. In addition, base-metal massive sulfide ores have high Cd, Ag, and Te contents, whereas tin–sulfide ores have elevated Ge, Ga, and Nb contents. This has stimulated the investment attractiveness of these deposits.     

20.

Zinc–germanium ores of the Tres Marias Mine,Chihuahua, Mexico     

Bernhardt Saini-Eidukat  Frank Melcher  Jerzy Lodziak 《Mineralium Deposita》2009,44(3):363-370

The Tres Marias carbonate-hosted Zn–Ge deposit in Chihuahua, Mexico contains sphalerite with the highest average Ge (960 ppm) and willemite with the highest reported Ge contents of Mississippi-Valley-type (MVT) deposits worldwide. This has prompted current exploration efforts to focus on the deposit as a high-grade source of germanium. The sulfide-rich ore type (>125,000 t at 20% Zn and 250 g/t Ge) contains Fe-rich botryoidal sphalerite (type I) associated with solid hydrocarbons. This type exhibits distinctive intimately intergrown lamellar texture of high-Fe sphalerite (average 9.9 wt.% Fe and 800 ppm Ge) and a somewhat less Fe-rich sphalerite phase (average 5.5 wt.% Fe and 470 ppm Ge). Reddish-brown banded sphalerite (type II, average 5.7 wt.% Fe and 1,320 ppm Ge) is subordinately followed by galena and pyrite. The sulfide-poor “oxidized” zinc ore (up to 50 wt.% Zn; 250 to 300 ppm Ge) is a fine-grained, often friable, alteration product of the sulfide ore and associated limestone and breccia host. While some areas are dominated by carbonates and sulfates, others are enriched in silicates such as hemimorphite and willemite. The gangue assemblage includes goethite, hematite, and amorphous silica or quartz. Minor wulfenite, greenockite, cinnabar, and descloizite also occur. Willemite occurs as interstitial replacement of sphalerite and fracture fillings in the oxidized ore and can be unusually rich in Pb (up to 2.0 wt.%) and Ge (up to 4,000 ppm). Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena by siliceous aqueous fluids. The Tres Marias deposit has hybrid characteristics consisting of a primary low-temperature MVT Ge-rich Zn–Pb sulfide ore body, overprinted by Ge-rich hemimorphite, willemite, and Fe oxide mineralization.     

Group	Ni (%)	Ga (ppm)	Ge (ppm)	Ir (ppm)
IC	6.1–6.8	42–54	85–250	0.07–10
IIE	7.5–9.7	21–28	62–75	0.5–8
IIIF	6.8–7.8	6.3–7.2	0.7–1.1	1.3–7.9

Distribution of indium in ores of some base metal and tin–sulfide deposits in Siberia and the Russian Far East

The study of base-metal massive sulfide and tin–sulfide deposits in Siberia and the Russian Far East has revealed that the indium content in ores exceeding the average statistical value at similar deposits worldwide could be economically important. Sphalerite and chalcopyrite and chalcopyrite, bornite, and sphalerite are the major indium carriers in the base-metal massive sulfide and tin–sulfide ores, respectively. In addition, base-metal massive sulfide ores have high Cd, Ag, and Te contents, whereas tin–sulfide ores have elevated Ge, Ga, and Nb contents. This has stimulated the investment attractiveness of these deposits.     

Zinc–germanium ores of the Tres Marias Mine,Chihuahua, Mexico

The Tres Marias carbonate-hosted Zn–Ge deposit in Chihuahua, Mexico contains sphalerite with the highest average Ge (960 ppm) and willemite with the highest reported Ge contents of Mississippi-Valley-type (MVT) deposits worldwide. This has prompted current exploration efforts to focus on the deposit as a high-grade source of germanium. The sulfide-rich ore type (>125,000 t at 20% Zn and 250 g/t Ge) contains Fe-rich botryoidal sphalerite (type I) associated with solid hydrocarbons. This type exhibits distinctive intimately intergrown lamellar texture of high-Fe sphalerite (average 9.9 wt.% Fe and 800 ppm Ge) and a somewhat less Fe-rich sphalerite phase (average 5.5 wt.% Fe and 470 ppm Ge). Reddish-brown banded sphalerite (type II, average 5.7 wt.% Fe and 1,320 ppm Ge) is subordinately followed by galena and pyrite. The sulfide-poor “oxidized” zinc ore (up to 50 wt.% Zn; 250 to 300 ppm Ge) is a fine-grained, often friable, alteration product of the sulfide ore and associated limestone and breccia host. While some areas are dominated by carbonates and sulfates, others are enriched in silicates such as hemimorphite and willemite. The gangue assemblage includes goethite, hematite, and amorphous silica or quartz. Minor wulfenite, greenockite, cinnabar, and descloizite also occur. Willemite occurs as interstitial replacement of sphalerite and fracture fillings in the oxidized ore and can be unusually rich in Pb (up to 2.0 wt.%) and Ge (up to 4,000 ppm). Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena by siliceous aqueous fluids. The Tres Marias deposit has hybrid characteristics consisting of a primary low-temperature MVT Ge-rich Zn–Pb sulfide ore body, overprinted by Ge-rich hemimorphite, willemite, and Fe oxide mineralization.