Crystal structure refinement of hendricksite,A Zn- and Mn-rich trioctahedral potassium mica: A contribution to the crystal chemistry of zinc-bearing minerals

Summary The crystal structure of hendricksite, a trioctahedral mica of biotite type, characterized by high Zn²⁺ and Mn²⁺ contents has been refined by least square methods. The structural formula is: (K_0.89Na_0.10Ba_0.04)(Mg_1.57Zn_0.54Mn _0.40 ²⁺ Fe _0.25 ²⁺ Al_0.07Ti_0.07Cr_0.01)(Si_2.92Al_1.08)O₁₀ (OH)₂. The space group isC2/m and the cell parameters are:a=5.340(2) Å,b=9.524(2) Å,c=10.235(3) Å, =100.07(2)^o, the cell volume isV=497.98 ų. The final unweightedR=0.072. Average cation-anion distances in polyhedra are: T–O=1.659 Å, M(1)–O=2.093 Å, M(2)–O=2.088 Å, A–O_long=3.316 Å and A–O_short=3.004 Å; A is the alkaline cation. The rotation angle of tetrahedra is =6.7°. The analysis of electron densities, of the dimensions and distorsions of polyhedra shows that Zn²⁺ is exclusively in octahedral sites; there is no order between six-fold coordinated cations. A comparison between the structural features of hendricksite and those of the two main end-members of biotites, phlogopite and annite, is presented.The effect of the strong covalence of Zn–O bonds is particularly visible on the dimensions and orientations of the thermal ellipsoids of octahedral sites M(1) and M(2) which contain zinc. In all the published structures of trioctahedral micas, the ellipsoids of cationic sites are uniaxial positive, elongated parallel toc ^*. In hendricksite, this is observed only for the two zinc-free sites (T and A; in the octahedra M(1) and M(2), which contain zinc, the ellipsoids are approximately uniaxial negative, flattened parallel toa, which is a unique situation.Zinc which habitually favours the tetrahedral coordinations with oxygen, enters the octahedra only, i.e. the chemically anisotropic sites, in hendricksite. The strong polarizability of Zn²⁺ is proposed to explain this behaviour.An examination of the behaviour of Zn²⁺ in other compounds shows that this situation is general, zinc favours chemically anisotropic sites and specially those adjacent to OH or H₂O.

---

Affinement de la structure cristalline de la hendricksite, mica trioctaédrique potassique riche en Zn et Mn; une contribution à la connaissance cristallochimique des minéraux zincifères

Résumé On a affiné par moindres carrés la structure de la hendricksite, mica trioctaédrique de type biotite, caractérisé par une teneur élevée en Zn²⁺ et Mn²⁺. La formule structurale de ce mica est: (K_0m89Na_0,10Ba_0,04)(Mg_1,57Zn_0,54Mn _0,40 ²⁺ Fe _0,25 ²⁺ Al_0,07Ti_0,07Cr_0,01)(Si_2,92Al_1,08)O₁₀(OH)₂. Le groupe spatial estC2/m et les paramètres de la maille:a=5,340(2) Å,b=9,254(2) Å,c=10,235(3) Å, =100,07(2)°; le volume de la maille estV=497,98 ų. Le résidu final non-pondéré estR=0,072. Les distances cation-anion moyennes dans les polyèdres sont les suivantes: T–O=1,659 Å, M(1)–O=2,093 Å, M(2)–O=2,088 Å, A–O_long=3,316 Å et A–O_court=3,004 Å où A désigne le cation alcalin. L'angle de rotation tétraédrique, =6,7°, est très semblable à celui de la phlogopite. L'analyse des densités électroniques, des dimensions et distorsions des polyèdres montre que Zn²⁺ est exclusivement en coordinance octaédrique et qu'il n'y a pas d'ordre entre les cations hexacoordonnés. On présente une comparaison des caractères structuraux de la hendricksite avec ceux des deux principaux pôles des biotites, la phlogopite et l'annite.L'effet de la forte covalence de la liaison Zn–O est particulièrement visible sur les dimensions et orientations des ellipsoides d'agitation thermique des deux sites octaédriques, sites zincifères. Dans toutes les structures de micas trioctaédriques publiées, les ellipsoides des sites cationiques sont uniaxes positifs, allongés parallèlement àc ^*, ce qui s' observe effectivement dans les deux sites non-zincifères (T et A) de la hendricksite, par contre, dans les octaèdres M(1) et M(2), qui contiennent le zinc, les ellipsoides sont approximativement uniaxes négatifs, applatis parallèlement àa, ce qui est une situation unique.Le zinc, qui se fixe généralement en sites tétraédriques dans les structures de type oxyde, occupe les sites octaédriques, c'est-à-dire les sites chimiquement anisotropes dans la hendricksite. La forte polarisabilité de Zn²⁺ est proposée pour expliquer ce comportement.Un examen du comportement de Zn²⁺ dans d'autres phases montre que cette situation est tout à fait générale, le zinc privilégiant les sites chimiquement anisotropes et en particulier ceux adjacents à OH où H₂O.

     

Isotope and trace element geochemistry of sediments from the Barbados Ridge-Demerara Plain region,Atlantic Ocean

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb${}^{206}\text{Pb}{}^{204}\text{Pb}$ up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and${}^{143}\text{Nd}{}^{144}\text{Nd}$ increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas.Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of “normal” depleted MORB.     

H-chondrites: Trace element clues to their origin

We have analyzed 10 H-chondrites for 20 trace elements, using RNAA. The meteorites included 4 of petrologic type 4 and 2 each of types 3, 5 and 6.The data show that H-chondrites are not isochemical. H3's are depleted by some 10% not only in Fe (Dodd, 1976), but also in the siderophiles Os, Re, Ir, Ni, Pd, Au, and Ge. Moreover, the abundance pattern of siderophiles varies systematically with petrologic type. As similar fractionations of REE have been observed by Nakamura (1974), it appears that both the proportions and compositions of the main nebular condensates varied slightly during accretion of the H-chondrites. Thus the higher petrologic types are independent nebular products, not metamorphosed descendants of lower petrologic types.Abundances of highly volatile elements (Cs, Br, Bi, Tl, In, Cd, Ar³⁶) correlate with petrologic type, declining by ≤ 10^?3 from Type 3 to Type 6. The trends differ from those for artificially heated Type 3's (Ikramuddinet al., 1977b; Herzoget al., 1979), but agree passably with theoretical curves for nebular condensation. Apparently the low volatile contents of higher petrologic types are a primary feature, not the result of metamorphic loss.The mineralogy of chondrites suggests that they accreted between 405 K (absence of Fe₃O₄) and 560 K (presence of FeS), and the abundances of Tl, Bi, and In further restrict this interval to 420–500 K. Accretion at 1070 ± 100 K, as proposed by Hutchisonet al. (1979, 1980), leads to some extraordinary problems. Volatiles must be injected into the parent body after cooling, which requires permeation of the body by 10¹¹ times its volume of nebular gas. This process must also achieve a uniform distribution of the less volatile elements (Rb, Cu, Ag, Zn, Ga, Ge, Sn, Sb, Se, F), without freezeout in the colder outer layers.Factor analysis of our data shows 3 groupings: siderophiles (Os, Re, Ir, Ni, Pd, Au, and Ge), volatiles (Ag, Br, In, Cd, Bi, and Tl) and alkalis (Rb and Cs). The remaining 5 elements (U, Zn, Te, Se, and Sb) remain unassociated.     

Petroleum isoprenoid hydrocarbons derived from catagenetic degradation of archaebacterial lipids

The three GC coeluting C₄₀ bis-phytanes with head-to-tail, tail-to-tail and head-to-head linkages considered to be archaebacterial markers, have been recognized in petroleum by enhanced mass-fragmentography. Supporting evidence has been obtained by the simultaneous occurrence of two C₂₁–C₂₄ series of isoprenoid and quasi-isoprenoid hydrocarbons that are supposedly formed during the catagenetic degradation of the isomeric C₄₀ isoprenoids. The C₂₁–C₂₄ quasi-isoprenoid hydrocarbons have been identified conclusively for the first time by comparison with authentic standards.     

Sites occupancy of Fe3+ in Garfield Nontronite: A spectroscopic study

New data on the structure of Garfield nontronite have been produced by the use of different spectroscopic techniques: Mössbauer spectroscopy, optical spectroscopy, X-ray absorption edges and EXAFS and NMR. The tetrahedral iron content is found to be no higher than 1 percent. All iron atoms belong to the octahedral sheet excluding the possibility of the presence of non crystallized phases. Some ambiguities remain about the coherence of the octahedral sheet because of the presence of two doublets in the Mössbauer spectrum and at least two lineshapes in NMR spectra of OH which correspond to different environments.     

A new type of active margin: the convergent-extensional margin,as exemplified by the Middle America Trench off Guatemala

The results of DSDP Legs 67 and 84, during which a transect of holes was drilled across the Middle America Trench off Guatemala, show no accretion at the front of that subduction zone since early Eocene time. The tectonic evolution of the trench includes extensional structure on the landward as well as the seaward trench slopes. The Guatemalan margin is proposed as the model of a new type of active margin, the convergent-extensional active margin (CE margin).     

Statistical analysis of isotopic ratios in MORB: the mantle blob cluster model and the convective regime of the mantle

A statistical examination of isotopic distributions for MORB from various ocean ridges leads to the “blob cluster model”, in which the oceanic crust accreting at ridges results from the mixing of two components within the ascending mantle. These are (1) upper mantle material and (2) discrete rising blobs of more radiogenic material. The blobs are fractionated to a variable degree and are distributed in the upper mantle circulation in a manner that is related to the spreading rate.(1) Themean values of the isotopic distributions allow us to calculate the probabilities of the two types of material within the mantle. The results show that theproportion of asthenospheric material in the mixtureincreases with the spreading rate, in agreement with the hypothesis of blob dilution within the upper mantle convection.Mass fluxes can be estimated for the rising blobs from these probabilities, which depend on the respective concentrations in the sources of the two types of material. If the blobs originate in the lower mantle, this flux estimation would suggest that a significant part of the lower mantle has been injected into the upper mantle during earth history.(2) Thestandard deviations of the distributions depend on the “efficiency” of the mixing process:the more imbricated are the asthenospheric and blob materials in the mixture,the smaller is theisotopic spread. This efficiency parameter is shown to increase with the spreading rate, as already suggested by previous comparisons between the East Pacific Rise and the Mid-Atlantic Ridge. Moreover, this feature may also be correlated with other data such as ridge bathymetric variations.     

Etude des minéralisations sulfurées du gisement de Salau,Pyrenées (France) et de ses environs

Résumé Les minéralisations du gisement de Salau, Pyrénées (France) comportent, outre la pyrrhotite et la scheelite, de la chalcopyrite, de l'arsénopyrite et de la sphalérite en phases accessoires. Ces sulfures ont été analysés à la microsonde électronique. — Les pyrrhotites sont les seuls sulfures à avoir subi l'influence de la mise en place de la rhyodacite. Les autres sulfures présentent une grande homogénéité et n'ont pas subi de modification liée à la mise en place du pluton. Les teneurs en fer des sphalérites, homogènes à l'intérieur d'un même niveau stratigraphique, mais différentes d'un niveau à l'autre, suggèrent une mise en place à plusieurs périodes sans remaniement ultérieur à leur dépôt.

---

Mineralisation of Salau deposit, Pyrénées (France) contain massive pyrrhotite and scheelite associated with chalcopyrite, arsenopyrite and sphalerite. Electron microprobe analyses of these sulfides have been systematically performed. — Pyrrhotites show a zonation with regard to the rhyodacite settlement. Other sulfides show a great homogeneity and are not disturbed by this settlement. Iron content of sphalerites, homogeneous inside a given stratigraphical level but different when the age of layers change, suggest several origins without further modification.

     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.