End-member Species Research Articles

Synthesis and characterization of Fe(III)-Fe(II)-Mg-Al smectite solid solutions and implications for planetary science

AbstractThis study demonstrates the synergies and limits of multiple measurement types for the detection of smectite chemistry and oxidation state on planetary surfaces to infer past geochemical conditions. Smectite clay minerals are common products of water-rock interactions throughout the solar system, and their detection and characterization provides important clues about geochemical conditions and past environments if sufficient information about their composition can be discerned. Here, we synthesize and report on the spectroscopic properties of a suite of smectite samples that span the intermediate compositional range between Fe(II), Fe(III), Mg, and Al end-member species using bulk chemical analyses, X-ray diffraction, Vis/IR reflectance spectroscopy, UV and green-laser Raman spectroscopy, and Mössbauer spectroscopy. Our data show that smectite composition and the oxidation state of octahedral Fe can be reliably identified in the near infrared on the basis of combination and fundamental metal-OH stretching modes between 2.1–2.9 μm, which vary systematically with chemistry. Smectites dominated by Mg or Fe(III) have spectrally distinct fundamental and combination stretches, whereas Al-rich and Fe(II)-rich smectites have similar fundamental minima near 2.76 μm, but have distinct combination M-OH features between 2.24 and 2.36 μm. We show that with expanded spectral libraries that include intermediate composition smectites and both Fe(III) and Fe(II) oxidation states, more refined characterization of smectites from MIR data is now possible, as the position of the 450 cm–1 absorption shifts systematically with octahedral Fe content, although detailed analysis is best accomplished in concert with other characterization methods. Our data also provide the first Raman spectral libraries of smectite clays as a function of chemistry, and we demonstrate that Raman spectroscopy at multiple excitation wavelengths can qualitatively distinguish smectite clays of different structures and can enhance interpretation by other types of analyses. Our sample set demonstrates how X-ray diffraction can distinguish between dioctahedral and trioctahedral smectites using either the (02,11) or (06,33) peaks, but auxiliary information about chemistry and oxidation state aids in specific identifications. Finally, the temperature-dependent isomer shift and quadrupole splitting in Mössbauer data are insensitive to changes in Fe content but reliability differentiates Fe within the smectite mineral structure.

Testing the effects of plant species loss on multiple ecosystem functions based on extinction scenarios

Ecosystem functions are threatened by continuing global loss of biodiversity. We simultaneously investigated three ecosystem functions and forage nutrient values following potential species extinction scenarios (dominant species removal, rare species removal, end-member species removal and random species removal) in a Mongolian grassland. ANPP, forage nutrient values, litter decomposition, and soil respiration were measured one and/or two years after plant removal. DNA samples of microorganisms extracted from the soil were subjected to metagenomics analysis. Finally, we calculated the multifunctionality, and examined the relationship of multifunctionality with plant and microorganism diversity. Among ecosystem functions, ANPP and litter decomposition rate decreased under random and rare species extinction scenarios, respectively, and forage quality increased when only dominant species had been removed. Diversity and species composition of soil microorganism were not affected by plant species richness or removal scenario. Only genus-level diversity of bacteria and ANPP were significantly and positively correlated with microbial diversity. Taken together, decreasing species richness of plants and soil organisms rarely impaired multifunctionality. Ecosystem functions were relatively robust to realistic disturbances and species extinction in natural grasslands. However, as each function responded differently to the different sets of species removed, the consequences of a realistic non-random extinction scenario for multiple ecosystem functions should be critical to the management of biodiversity loss caused by different disturbances.

Chemical Composition of Mn- and Cl-Rich Apatites from the Szklary Pegmatite, Central Sudetes, SW Poland: Taxonomic and Genetic Implications

Although calcium phosphates of the apatite group (apatites) with elevated contents of Mn are common accessory minerals in geochemically evolved granitic pegmatites, their Mn-dominant analogues are poorly studied. Pieczkaite, M1Mn2M2Mn3(PO4)3XCl, is an exceptionally rare Mn analogue of chlorapatite known so far from only two occurrences in the world, i.e., granitic pegmatites at Cross Lake, Manitoba, Canada and Szklary, Sudetes, SW Poland. In this study, we present the data on the compositional variation and microtextural relationships of various apatites highly enriched in Mn and Cl from Szklary, with the main focus on compositions approaching or attaining the stoichiometry of pieczkaite (pieczkaite-like apatites). The main goal of this study is to analyze their taxonomical position as well as discuss a possible mode of origin. The results show that pieczkaite-like apatites represent the Mn-rich sector of the solid solution M1(Mn,Ca)2M2(Mn,Ca)3(PO4)3X(Cl,OH). In the case of cation-disordered structure, all these compositions represent extremely Mn-rich hydroxylapatite or pieczkaite. However, for cation-ordered structure, there are also intermediate compositions for which the existence of two hypothetical end-member species can be postulated: M1Ca2M2Mn3(PO4)3XCl and M1Mn2M2Ca3(PO4)3XOH. In contrast to hydroxylapatite and pieczkaite, that are members of the apatite-group, the two hypothetical species would classify into the hedyphane group within the apatite supergroup. The pieczkaite-like apatites are followed by highly Mn-enriched fluor- and hydroxylapatites in the crystallization sequence. Mn-poor chlorapatites, on the other hand, document local contamination by the serpentinite wall rocks. We propose that pieczkaite-like apatites in the Szklary pegmatite formed from small-volume droplets of P-rich melt that unmixed from the LCT-type (Li–Cs–Ta) pegmatite-forming melt with high degree of Mn-Fe fractionation. The LCT melt became locally enriched in Cl through in situ contamination by wall rock serpentinites.

A spreadsheet for calculating normative mole fractions of end-member species for Na-Ca-Li-Fe2+-Mg-Al tourmalines from electron microprobe data

This work presents a spreadsheet that calculates the mole fractions of end-member components for simple Na-Ca-Li-Mg-Fe2+-Al tourmalines from electron microprobe data. The input includes the B2O3 concentration obtained either from direct analysis or by estimation on the basis of stoichiometry. The concentration of Li2O can either be input from other analysis or estimated by the spreadsheet. The spreadsheet does not address the mole fractions of Cr, V, oxidized or deprotonated tourmaline species, nor account for species involving tetrahedral boron or aluminum. Therefore, the spreadsheet is not a comprehensive tool that includes all IMA approved tourmaline species, and so is not intended for naming tourmalines according to IMA convention. The present method includes a useful subset of end-member species that can be described simply from electron microprobe data and so, akin to a normative mineralogical analysis for rock composition, the calculations are intended to provide a normative result that serves as simple basis for comparing tourmalines that is more direct than names derived from the most abundant species present.

In situ X-ray powder diffraction studies of hydrogen storage and release in the Li–N–H system

We report the experimental investigation of hydrogen storage and release in the lithium amide-lithium hydride composite (Li-N-H) system. Investigation of hydrogenation and dehydrogenation reactions of the system through in situ synchrotron X-ray powder diffraction experiments allowed for the observation of the formation and evolution of non-stoichiometric intermediate species of the form Li1+xNH2-x. This result is consistent with the proposed Frenkel-defect mechanism for these reactions. We observed capacity loss with decreasing temperature through decreased levels of lithium-rich (0.7 ≤ x ≤ 1.0) non-stoichiometric phases in the dehydrogenated material, but only minor changes due to multiple cycles at the same temperature. Annealing of dehydrogenated samples reveals the reduced stability of intermediate stoichiometry values (0.4 ≤ x ≤ 0.7) compared with the end member species: lithium amide (LiNH2) and lithium imide (Li2NH). Our results highlight the central role of ionic mobility in understanding temperature limitations, capacity loss and facile reversibility of the Li-N-H system.

Phase relations in garnet-bearing metabasites of prehnite-pumpellyite facies from the Darbut-Sartuohai ophiolite, Western Junggar of Xinjiang, China

Previous petrogenetic grids for very low grade metamorphism do not apply to garnet-bearing prehnite-pumpellyite facies rocks. Garnet-bearing metabasites with Act – absent of prehnite-pumpellyite facies have been found in the Darbut-Sartuohai ophiolite, Xinjiang, China. Results of thermodynamic calculation in the CMASH system using the internally consistent mineral thermodynamic database of Berman (1988) show that equilibria reactions among the end-member species in mineral paragenesis of Pmp-Prh-Grs-Zo-Chl-Qtz intersect at a pressure of 4.75 kbar and temperature of 350 °C. The association of grossular-rich garnet and pumpellyite occurs at pressures and temperatures similar to the Pmp-Act facies. Based on the petrogenetic grid derived in this study, peak metamorphic conditions for metabasites from the Darbut-Sartuohai ophiolite are 310 to 330 °C, and 3.0 to 4.0 kbar, which are affected by the substitution of Fe3+Al−1. This study shows that grossular-rich garnet can appear in metabasites of the prehnite-pumpellyite facies, but it depends on the substitution between Fe3+ and Al in the CMASH+Fe3+ system.

Modelling of some structural parameters of tourmalines on the basis of their chemical composition. I. Ordered structure model

This study models the mean sizes of X, Y, Z, B and T sites as well as the unit-cell parameters of tourmalines on the basis of their chemical compositions, using previously determined relations between the mean bond lengths in co-ordination polyhedra and the cation populations in those sites. For the octahedral sites of Al-rich tourmalines, these relations also take into account the possible modifying influences of the IInd co-ordination shells. For Al-poor tourmalines, the following relationships were determined: Fe 3+ , Mg 2+ and Ti 4+ ions supplementing the deficit of aluminium located at the Z octahedra have an effect on the mean size of the Z site, and these ions have a modifying influence on the adjacent Y sites. For a set of 43 tourmalines from various localities, representing various members of this mineral group, the observed unit-cell parameters were compared with the calculated values. The standard errors SE of the models: a calc . = K a a obs. and C calc . = k c c obs . are 0.0 13 A and 0.008 A, respectively, and the k a , k c coefficients are close to the theoretical value of 1 within the limits of a statistical error se = 0.0001-0.0002. These values suggest a highly satisfactory agreement of the measured and modelled values and indicate that the determined model equations can be used to predict the structural parameters of tourmalines. On this basis, the model predicts the structural characteristics of all end-member species known in the tourmaline group, assuming the ordering of octahedral ions between Y and Z sites. In some (Fe 3 +,Al)-rich tourmalines (buergerites and schorls) and Al-rich dravites small differences have sometimes been noted between the observed and predicted values of and mean sizes, as well as the a and c unit-cell parameters; the differences suggest a limited disordering of Fe 3+ and Al or Mg and Al between Y and Z sites.

Age and growth of Electrona antarctica (Pisces: Myctophidae), the dominant mesopelagic fish of the Southern Ocean

Numerically and in biomass, the lanternfish Electrona antarctica is the dominant fish in the vast pelagic region of the Southern Ocean bounded on the north by the Antarctic Convergence and in the south by the Antarctic continental shelf. It is an important krill predator, and in turn is important in the diets of flighted and swimming seabirds. Further, it is the southernmost and coldest-dwelling representative of the globally distributed fish family Myctophidae. The present study was undertaken to estimate the species' growth rate and average life span, to incorporate the information in a basic energy budget, and to compare the growth of E. antarctica with more northerly confamilials. Fishes were aged using primary growth increments that were resolved on sagittal otoliths using three sequential techniques: thin-section grinding and polishing, etching, and scanning electron microscopy (SEM). Based on increment width (0.8 to 1.2 μm), continuity, and previous studies on confamilials, the microincrements were assumed to be deposited on a daily basis. Montages of SEM photomicrographs were constructed for each sagitta to allow the daily rings to be counted over the entire life span of 31 individuals representing the entire size range of the species. Results suggest a larval stage of 30 to 47 d and a maximum life span of 3.5 yr, with females growing faster than males in the last 1.5 yr of life and reaching a larger maximum size. Construction of a simple energy budget using the best information available suggests that a surplus of energy is available to support the observed growth rates (0.05 to 0.07 mm d−1). The results of the present study contrast markedly with previous estimates of an 8 to 11 yr maximum age for E. antarctica. These results provide important data addressing the ecology and population dynamics of the pelagic Antarctic ecosystem. E. antarctica is the end-member species in the continuum of vertically migrating myctophids that extend from the equator to the polar circle. Its growth rate is consonant with that of all other myctophid species examined using primary growth increments to determine age. The present study, in conjunction with earlier studies, suggests that growth rates of mesopelagic species are far higher than previously thought.