Analytical Electron Microscopy Analyses Research Articles

Ammonium-bearing micas in very low-grade metapelites: micro- and nano-texture and composition

ABSTRACTThe present study examines the micro- and nano-texture and composition of ammonium-bearing and potassium micas in very-low grade metamorphic black Silurian shales from the SE Iberian Range (NE Spain). Two organic-rich shales were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron energy loss spectroscopy (EELS). The XRD showed the presence of two populations of micas: pure K micas with d001 = 9.98 Å and ammonium-bearing micas with larger d001 values (10.08 Å and 10.05 Å). The latter values indicate NH4 contents between 13 and 29% in the interlayer, which was confirmed by IR. Interstratifications of smectite and mica layers in the mica packets were not detected by XRD and TEM. Mica packets with sizes ranging from 100 to 250 Å show disordered polytypes and (001) lattice fringes that reflect the presence of K- and NH4-bearing layers (9.9–10.2 Å).The combination of AEM and EELS analyses on powdered and lamellar samples indicates that micas have typical dioctahedral compositions with highly variable K contents. This variation in K is consistent with the presence of K and NH4 in the interlayers, even though the NH4 and K are not distributed homogeneously; rather they are segregated in nm-sized domains in the mica interlayer.

Powder XRD and TEM study on crystal structure and interstratification of Zn-chlorite (baileychlore)

Baileychlore is Zn-end member trioctahedral chlorite, named by Audrey C. Rule and Frank Radke in 1988 for the honor of Professor Sturges W. Bailey of the University of Wisconsin – Madison, USA. Baileychlore occurs as dark green chlorite on calcite veins from garnet-vesuvianite skarn clasts at Red Dome ore deposit, Chillagoe, Queensland, Australia. The baileychlore has been studied by using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray energy-dispersive analytical electron microscopy analyses to determine crystal structure and interstratified layers. Baileychlore with stacking disorder displays streaking reflections of 0k0 (≠6n) hhl (h ≠ 3n). Unit-cell parameters for baileychlore (type I polytype) with a space group of C$ \bar 1$ are: a = 5.351(3), b = 9.266(5), c = 14.418(8) Å, α = 89.741(3)°, β = 96.741(4)°, and γ = 90.122(2)°. The strong lines of the measured XRD pattern [d(Å)(I)(hkl)] are: 14.331(7.151)(90.5)(002); 4.574(23.2)(1$ \bar 1$0, 11$ \bar 1$); 3.572(38.5)(004); 2.653(31.4)($ \bar 1$31, 200, 13$ \bar 1$); 2.406(49.4)(202, $ \bar 1$33, 13$ \bar 3$); 1.543(27.6)($ \bar 3$31, 060, 33$ \bar 1$), respectively. Reitveld refinement provides a composition (Zn2.49Al0.09Fe2+ 0.09□0.33)0.61− for the octahedral sheet and (Si3.53Al0.47)0.47− for the tetrahedral sheets within the 2:1 layer with (Al1.08Fe1.08Mg0.84)1.08+ for the interlayer sheet. The refinement results indicate that baileychlore is an intergrowth of type I and II polytypes. High-resolution TEM images show stacking disorder of baileychlore with small amount of isolated smectite layers.

On the Chemical Composition of Sepiolite and Palygorskite

AbstractMany studies of the chemical composition of sepiolite and palygorskite have been carried out using analytical electron microscopy (AEM). According to the literature, a compositional gap exists between sepiolites and palygorskites, but the results presented here show that they may all be intermediate compositions between two extremes. The results of >1000 AEM analyses and structural formulae have been obtained for the samples studied (22 samples of sepiolite and 21 samples of palygorskite) and indicate that no compositional gap exists between sepiolite and palygorskite. Sepiolite occupies the most magnesic and trioctahedral extreme and palygorskite the most aluminic-magnesic and dioctahedral extreme. Sepiolite and palygorskite with intermediate compositions exist between the two pure extremes: (1) sepiolite with a small proportion of octahedral substitution; (2) palygorskite with a very wide range of substitution (the pure dioctahedral extreme is unusual); and (3) intermediate forms, Al-sepiolite and Mg-palygorskite with similar or the same chemical composition. The chemical compositions of the intermediate forms can be so similar that a certain degree of polymorphism exists between Al-sepiolite and Mg-palygorskite.

Association of individual soil mineral constituents and heavy metals as studied by sorption experiments and analytical electron microscopy analyses

Sorption characteristics of bulk soil samples and discrete soil mineral constituents were studied by Cu, Zn and Pb batch sorption experiments and analytical electron microscopy analyses. Copper and zinc sorbed mostly on soil mineral constituents, while lead was associated mainly to soil organic matter. Additionally, the competitive situation resulted in increase of the role of iron oxides in Pb sorption. Close association of iron oxides and silicates resulted in significant change in their sorption capacities for all the studied metals. The alkaline conditions due to the calcite content in one of the studied soil samples resulted in both increased role of precipitation for Pb and Cu and elevated sorption capacity for Cu by discrete mineral particles. Using the analytical electron microscopy analyses the sorption characteristics of metals were supported by particular data. When the methods used in this study are combined, they become an extremely powerful means of getting a deeper insight into the soil–metal interaction.

Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal–mineral interactions in soils.

Origin of mixed-layered (R1) muscovite-chlorite in an anchizonal slate from Puncoviscana Formation (Salta Province, Argentina)

AbstractMica-chlorite mixed-layering was identified by X-ray diffraction (XRD) as a major or subordinate constituent in several slates of the Puncoviscana Formation from Sierra de Mojotoro (Eastern Cordillera, NW Argentina). In order to determine the crystallochemical characteristics of these mixed-layered sequences and interpret their petrological meaning, anchizonal slate P90 was chosen for TEM observations. In this slate, dioctahedral mica and chlorite form interleaved phyllosilicate grains (IPG) or stacks, up to 110 um long, preferentially oriented with (001) planes at a high angle to the slaty cleavage but also oblique to S0.In agreement with XRD results, the main phyllosilicates identified by transmission electron microscopy (TEM) were dioctahedral mica and random mixed-layer muscovite-chlorite, with chlorite in subordinate amounts and scarce smectite. In the lattice-fringe images of mixed-layer packets, a sequence of irregular stacking that produced apparent 24 Å (10 + 14) layers was observed, but it was frequently possible to distinguish the 10 Å layers from adjacent 14 Å layers. In nearly all packets, 14 Å layers prevail, exhibiting 14 Å:10 Å ratios between 1:1 and 3:1. Some elongated lenticular fissures which are probably a consequence of layer collapse caused by the TEM vacuum were identified in these packets. The straight, continuous appearance of lattice fringes plus the scarce evidence of collapsed layers identified suggest that these packets correspond principally to mixed-layer muscovite-chlorite, which is confirmed by analytical electron microscopy analyses. However, smectite-like layers are probably the third component of some of these mixed-layer sequences, which may account for their high Si and low (Fe + Mg) contents, their low interlayer charge in relation to theoretical interlayer muscovite-chlorite, and for the presence of Ca in the interlayer site.Textural relationships between chlorite and muscovite packets in IPG along with the observed transformations from 14 Å to 10 Å along the layer, is compatible with a prograde metamorphic replacement of chlorite in stacks by dioctahedral mica layers, probably in the presence of an aqueous fluid.

Synthesis of Kaolinite with a High Level of Fe3+ for Al Substitution

AbstractFe-rich kaolinites were synthesized at 225°C in distilled water from gels with different Fe/Al ratios (0.15, 0.25, 0.35) and with Si/(Al + Fe) = 2. X-ray diffraction patterns of the reaction products showed that kaolinite was the only long-range crystalline phase synthesized. Analytical electron microscopy analyses of individual particles and Fourier transform infrared spectra indicated that Fe3+ was isomorphously incorporated into the kaolinite octahedral sheet and that tetrahedral substitution did not occur. The Fe content hosted in the synthetic kaolinites was similar to that incorporated into its corresponding starting gel. The highest Fe content in the particles reached 30 mol.% of the octahedral occupancy. Increases in the b parameter are proportional to increases in Fe for Al substitution. The extent of isomorphic substitution of Al by Fe is the highest ever reported for both natural and synthetic samples. At the nano-scale, there is no evidence of discontinuity in the solid-solution between the Si2Al2O7 and Si2Al1.4Fe0.6O7 end-members, such as short-range disorder or clustering of Fe and Al in domains.

Transmission electron microscopy study of very low-grade metamorphic evolution in Neoproterozoic pelites of the Puncoviscana formation (Cordillera Oriental, NW Argentina)

AbstractThe Puncoviscana Formation, largely cropping out in NW Argentina, is mainly composed of a pelite-greywacke turbidite sequence affected by incipient regional metamorphism and polyphase deformation. Metapelites, composed mainly of quartz, albite, dioctahedral mica and chlorite, were sampled in the Lules-Puncoviscana and Choromoro belts. Lattice-fringe images, selected area electron diffraction and analytical electron microscopy analyses, coupled with previous data from white mica crystallinity index, indicate a state of reaction progress for Puncoviscana slates consistent with medium anchizone- to epizone-grade metamorphism. The 2Mpolytype prevails in dioctahedral micas, coexisting in a few cases with the 1Mdpolytype as a consequence of lack of equilibrium. The 2Mpolytype coexists with 3Tin two slates and long-range four-layer and ten-layer stacking sequences were identified in another sample. Samples with 3Tand long-range stacking sequences presentbvalues characteristic of intermediate–high pressure metamorphism and ordered chlorites (1L, 2L, 3Land 7L) prevail.Based on the Si contents of dioctahedral micas and considering peak temperatures of ∼350 –400ºC, pressures from 5 kbar and 5 –7 kbar were derived for metapelites from the Lules- Puncoviscana and Choromoro belts, respectively. These values agree with facies series derived from thebvalues. Micas with a wide range of phengitic substitution, as evidenced by Fe + Mg and Si contents, coexist. These variations could not arise from the disturbing effect of detrital white K-mica because TEM evidence indicates that they are absent or represent <10% of the mica population. Thus, compositional variations suggest that dioctahedral micas of individual slates crystallized at different pressure conditions in response to theP-Tpath of the metamorphism. Moreover, in several biotite-free slates the illite crystallinity (IC) values lead to an underestimation of the metamorphic grade attained in these rocks.The coexistence of IC corresponding to anchizone and the occurrence of biotite in some slates and felsic metavolcanic rocks intercalated in the Puncoviscana metasediments are interpreted to be the result of a metamorphic path including a relatively high-pressure/ low-temperature (HP/LT) event, followed by a lower-pressure overprint possibly at higher temperatures than the HP/LTevent. Small micas formed during the high-pressure stage would prevail in the <2 mm fraction, producing anchizone IC.

Influence of Cation Size on the Curvature of Serpentine Minerals: HRTEM-AEM Study and Elastic Theory

AbstractThe influence of cation size on the misfit between the tetrahedral and the octahedral sheets of serpentine layers, and thus on the curvature of serpentine minerals, has been studied using an experimental approach, based on scanning and high-resolution transmission electron microscopies (SEM and HRTEM, respectively) coupled with analytical electron microscopy (AEM), and a theoretical approach, based on the elastic theory of thin plates and the surface stress concept.Various Ni3(Si,Ge)2O5(OH)4 serpentine syntheses were prepared, with progressive tetrahedral substitution for Si by the larger Ge ion, the ratio Ge/(Si + Ge) ranging from 0 to 100%. Other parameters (temperature, time duration, water pressure) were fixed. From SEM-HRTEM observations and AEM analyses of all samples, two types of serpentine minerals were characterized: (1) curved structures of tubular or ‘roman-tile’ shape (curvature radius of 10 nm for 0% Ge, increasing with the Ge content), when the Ge tetrahedral content is <25%; (2) perfectly plane structures, with hexagonal or triangular shape (view normal to the layers), for greater Ge contents. These results prove the direct influence of cation size on the crystal curvature.From a theoretical point of view, a single serpentine layer with a misfit between its tetrahedral and octahedral sheets can be considered as an elastic thin plate subjected to two different surface stresses, σ+ and σ−, on its two faces. The difference σ+ − σ− between these two surface stresses was calculated from the above geometrical misfit, and the curvature of the serpentine layer was related to σ+ − σ−, according to the elastic theory of thin plates. The calculated curvature radii, and the Ge content of transition from curved to plane structures, are in agreement with the above observed values. Curved serpentine crystals may then be considered as a stacking of such elastically curved single serpentine layers.

Microstructural characterization of 5 to 9 pct Cr-2 pct W-V-Ta martensitic steels

The microstructure of 9Cr-2W-0.25V-0.1C (9Cr-2WV), 9Cr-2W-0.25V-0.07Ta-0.1C (9Cr-2WVTa), 7Cr-2W-0.25V-0.07Ta-0.1C (7Cr-2WVTa), and 5Cr-2W-0.25V-0.07Ta-0.1C (5Cr-2WVTa) steels (all compositions are in wt pct) have been characterized by analytical electron microscopy (AEM) and atom probe field ion microscopy (APFIM). These alloys have potential applications in fusion reactors because they exhibit reduced neutron activation in comparison to the conventional Cr-Mo steels. The matrix in all four alloys was 100 pct martensite. The precipitate type in the steels depended primarily on the chromium level in the alloy. In the two 9Cr steels, the stable phases were blocky M23C6 and small spherical precipitates previously identified as MC. The two lower-chromium steels contained blocky M7C3 and small needle-shaped carbonitrides in addition to M23C6. The AEM and APFIM analyses revealed that, in the steels containing tantalum, the majority of the tantalum was in solid solution. With the exception of a few of the small spherical precipitates in low-number densities in the 9Cr-2WVTa, none of the other precipitates contained measurable tantalum. The experimentally observed phases were in agreement with those predicted by phase equilibria calculations using the ThermoCalc software. However, a similar match between the experimental and predicted values of the phase compositions did not occur in some instances. Atom probe analyses directly confirmed the crucial role of trace amounts of nitrogen in the formation of vanadium-rich carbonitrides as predicted by thermodynamic equilibrium calculations.

Determination of 25 elements in the complex oxide mineral zirconolite by analytical electron microscopy

In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, k ATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: M8Ca 2+ + M5,6Ti 4+→ M8REE 3+ + M5,6(Al,Fe) 3+ and M8Ca 2+ + M5,6Ti 4+→ M8(Th,U) 4+ + M5,6 (Mg,Fe) 2+.

Compositional Variation in Clay Mineral Fraction of Fine and Coarse-Grained Units in Westwater Canyon Member (Morrison Formation, San Juan Basin, New Mexico): ABSTRACT

Smectites and mixed-layer illite/smectite clays from a suite of core samples drawn from the Westwater Canyon Member of the Morrison Formation (USGS borehole S6) have been examined using analytical electron microscopy (AEM) and x-ray diffraction. Samples from 784 and 808 m deep are fine and coarse-grained, respectively. An intermediate sample (806-m depth) is a sandy siltstone with conspicuous shale intraclasts. The fine and mixed grain-size samples are characterized by illitic clays (14% expandable, ordered; 21% expandable, random). The coarse-grained sample is, by contrast, highly expandable (96%). All AEM analyses were performed at {minus}150{degree}C to minimize electron beam damage and retard loss of volatile interlayer cations. Interlayer sites for clays in all of these samples are dominated by Na and K with minor Ca. Mixed-layer clays of the fine-grained and intraclast-bearing units are characterized by high K/Na in interlayer sites, and clays of the coarse-grained sample include Na-rich varieties. All of the clays are dioctahedral. The octahedral chemistry of each sample is dominated by Al, Mg, and divalent Fe. The proportion of Al to divalent cations in the octahedral layer ranges from three to four in all samples. Charge on the TOT layer of the clays spans the expected range frommore » illite to smectite. Some of this variation may indicate that detrital illites or mixed-layer materials were present in the fraction analyzed. These data may reflect compositional variation of the diagenetic fluids that percolated through fine and coarse-grained units of the Westwater Canyon member.« less