Boron has been shown to be a useful trace element in clay-mineralization reactions, raising the possibility that B studies may provide a means to investigate environmental controls on palagonitization. The objective of the present study was to address calibration, matrix effects, and B exchangeability issues such that meaningful secondary ion mass spectrometry (SIMS) microanalysis of B in thin sections of palagonite will be feasible. Silver Hill illite (IMt-1) was found to be a suitable calibration reference material, based on compositional similarity, relatively high B content, and ease of mounting on thin-section samples for SIMS microanalysis. Matrix effects of borated sideromelane and illite were compared and found to be similar, confirming previous studies which showed no matrix effects for B among minerals. Boron substitutes for Si in tetrahedral sites and also can be adsorbed in exchangeable sites of 2:1 clay minerals. Similarly, B can be found in tetrahedral and exchangeable sites within palagonite, which consists of both layered and amorphous volumes. In order to measure tetrahedral B content and isotopic ratio in the palagonite, exchangeable B was removed by soaking sample thin sections in a 1 M NH4Cl solution until exchangeable cation concentrations were constant. Treated samples showed decreases in B content and isotopic ratio with exchange. Extraction of exchangeable B permits the direct measurement of tetrahedral B content and isotopic ratio. The exchange technique devised and tested here should have broad applicability to thin-section microanalysis of B in clay and clay-like materials where cation exchange can be used for surface-analytical techniques. The present study represents an initial attempt to address samplepreparation, calibration, and potential matrix-effects problems for analyses by SIMS. Further refinements may improve the accuracy of the measurements, but the results presented here indicate that meaningful measurements are possible.

Correlative microscopy approaches are attracting considerable interest in several research fields such as materials and battery research. Recent developments regarding X-ray computer tomography have made this technique available in a compact module for scanning electron microscopes (SEMs). Nano-computed tomography (nanoCT) allows morphological analysis of samples in a nondestructive way and to generate 2D and 3D overviews. However, morphological analysis alone is not sufficient for advanced studies, and to draw conclusions beyond morphology, chemical analysis is needed. While conventional SEM-based chemical analysis techniques such as energy-dispersive X-ray spectroscopy (EDS) are adequate in many cases, they are not well suited for the analysis of trace elements and low-Z elements such as hydrogen or lithium. Furthermore, the large information depth in typical SEM-EDS imaging conditions limits the lateral resolution to micrometer length scales. In contrast, secondary ion mass spectrometry (SIMS) can perform elemental mapping with good surface sensitivity, nanoscale lateral resolution, and the possibility to analyze even low-Z elements and isotopes. In this study, we demonstrate the feasibility and compatibility of a novel FIB-SEM-based correlative nanoCT-SIMS imaging approach to correlate morphological and chemical data of the exact same sample volume, using a cathode material of a commercial lithium battery as an example.

Application of atom probe tomography (APT) and 1.5D secondary ion mass spectrometry (SIMS) as complimentary techniques to study fin sidewall doping by plasma implantation (PLAD) is the focus of this paper. Unlike planar transistors, characterization of 3D devices both by SIMS and APT requires sample preparation via trench backfill with α-Si, or other material, via chemical vapor deposition or atomic layer deposition process due to high aspect ratio of test structures. Certain artifacts with adverse impacts on quantitative results encountered in this study are discussed.

Sazhinite-(La) is a new mineral from the Aris phonolite, Windhoek, Namibia. It occurs in vesicles within the phonolite, together with other species crystallized from late-stage hydrothermal fluids: natrolite, aegirine, microcline, apophyllite, sphalerite, analcime, fluorite, villiaumite, hydroxylapatite, galena, makatite, quartz, eudialyte, kanemite, tuperssuatsiaite and korobitsynite. Sazhinite-(La) forms small euhedral crystals up to 1 mm long and 0.4 mm wide, elongated along [001] and flattened on (010), exhibiting the forms {h0l}, {100} and {001}. It has good cleavage parallel to {010} and {001}. Twinning was not observed. Crystals are brittle with a Mohs hardness of 3, creamy white with a white streak, vitreous to pearly lustre, and translucent to transparent. In plane-polarized light, crystals are colourless with a = Z, b = Y, c = X. It is biaxial positive with α = 1.524, β = 1.528, γ = 1.544, all ±0.002, 2Vz(obs) = 46(1)°, and 2Vz(calc.) = 53.6°.

Sazhmite-(La) is orthorhombic Pmm2, a = 7.415(2), b = 15.515(3), c = 7.164(1) Å, and V = 824.2 Å3. One crystal was studied by X-ray diffraction, electron microprobe and secondary ion mass spectrometry (SIMS) microanalysis, leading to the average composition (Na2.87K0.02Sr0.01)Σ2.90 [La0.41Ce0.35Pr0.02Nd0.04(Sm,Gd,Dy,Er,Yb)Σ0.01Th0.09U0.01Y0.01Zr0.01Ca0.08Li0.01]Σ1.04 (S15.87S0.06B0.01) (O14.86F0.14).(H2O)2.

Weighted full-matrix least-squares refinement on 3369 reflections yielded Rall = 3.8%. The structure is built of corrugated [Si6O15]6- layers linked by [7]-coordinated REE and R4+ cations. This framework leaves channels that contain three [5]- and [6]-coordinated Na cations per formula unit that compensate for the residual charge on the silicate layers. The SIMS analyses confirm a Na content of 3 atoms per formula unit, leading to an ideal formula of Na3LaSi6O15(H2O)2. The third Na atom is bonded to H2O groups and therefore the total content of both Na and H2O may be reduced to 2 and 1 per formula, respectively. The depletion in Na allows for the entrance of high-charge cations such as Th4+.

The need in geology for in situ U-Pb age determinations of minerals is illustrated by two examples: the internal age dispersion developed within the zircon SL13 shortly after original crystallization, and the occurrence within minerals of old cores and later overgrowths. SL13 contains rare μm-sized patches of unsupported radiogenic Pb and a mainly bimodal distribution of 206Pb/238U ages otherwise. Both observations are consistent with original crystallization at 580 Ma and Pb loss at 565 Ma. Age precision is controlled by the ions counted for radiogenic Pb, and varies with instrumental sensitivity, age and U contents of the target. Laser-ablation ICPMS has similar spatial resolution and sensitivity to SIMS but consumes more sample because of much greater hole-depth in practice. Like SIMS, the measured Pb+/U+ is biased and also changes with depth so comparison with a standard mineral is necessary. Analyses of reference zircons reported here indicate that the reproducibility of Pb/U ages by ICPMS is limited by residual bias, not ion counting errors. For multipurpose ICPMS at least, the Hg background at mass 204 prohibits the measurement of 204Pb for common Pb estimation. A third micro-analytical method, ‘CHIME’, and future developments in SIMS and ICPMS are discussed briefly.

Oxygen isotope measurements using SIMS and laser-fluorination methods confirm the presence of concentric and sector zoning in low-temperature (200°C to <400°C) hydrothermal quartz from Alpine veins. While concentric zoning is most readily explained by changes in the chemical composition of the fluid or temperature of crystallization, the reasons for sector zoning are more difficult to explain. Relative enrichment in 18O for crystallographically different sectors of quartz corresponds to m >r >z. Sector zoning is, however, largely limited to the exterior zones of crystals and/or to crystals with large Al (>1000 ppm) and trace element contents, probably formed at temperatures <250°C. Differences in δ18O between the prismatic (m) relative to the rhombohedral (r and z) growth sectors of up to 2% can be explained by a combination of a face-related crystallographic and/or a growth rate control. In contrast, isotopic sector zoning of up to about 1.5% amongst the different rhombohedral faces increases in parallel with the trace element content and is likely to represent disequilibrium growth. This is indicated by non-systematic, up to 2%, differences within single growth zones and the irregular, larger or smaller, δ18O values (of several permil) of the exterior compared to the inner zones of the same crystals. Disequilibrium growth may be related to the large trace element content incorporated into the growing quartz at lower temperatures (<250°C) and/or be related to fluid-vapour separation, allowing crystal growth from both a vapour as well as a liquid phase.

Authigenic quartz overgrowths and hydrothermal quartz crystals from locations in Oman and Switzerland have been investigated with SIMS, EPMA, SEM-CL and SEM-CC. All techniques reveal similar zonation patterns with SEM-CL having the best resolution followed by SEM-CC, EPMA and finally SIMS. The observed zonations reflect chemical and/or physical changes during growth in the precipitation environment or disequilibrium precipitation at the crystal surface (i.e. sectoral and intrasectoral zonation). Based on the total Al content, two types of authigenic quartz are distinguishable. When the Al concentration is <500 μg g–1 the predominant CL emission is at ~630 nm; in such quartzes, SEM-CL and SEM-CC are directly correlated, and signal intensities drop as a function of increasing Al concentration. In contrast, authigenic quartz with Al concentrations between 500 μg g–1 and 1000 μg g–1 has CL emission maxima at both ~630 nm and ~380—400 nm, at which point the panchromatic SEM-CL and SEM-CC intensities become decoupled.

Diamonds from George Creek, Colorado, preserve complex intergrowth textures between two major growth generations: homogeneous diamond with yellow-buff cathodoluminescence (CL); and diamond with blue-green CL and local growth zonation. Secondary-ion mass spectrometry (SIMS) has revealed large variations in N concentration and C isotope composition within these diamonds. Even within single stones, N contents and δ13C values can vary from 0 to 750 ppm and 0 to −20‰ respectively. These variations are similar to those recorded elsewhere for entire diamond suites. The CL characteristics correlate directly with N: diamond with yellow-buff CL has uniform N contents, whereas the zoned diamond has bright blue CL bands with high N (50–750 ppm) and dark blue or green CL bands with low N (0–20 ppm). These bands are too narrow (10–5 µm) for analysis by IR spectroscopy. δ13C also varies between the two growth generations in any one diamond plate, and to a lesser extent within these generations, but shows no consistent correlations with either CL or N. The George Creek stones preserve evidence of extreme temporal and/or spatial variations in both δ13C and N concentrations during the period of diamond growth, but the factors controlling N content during diamond growth did not control δ13C.

The hindguts of lower termites harbor highly diverse, endemic communities of symbiotic protists, bacteria, and archaea essential to the termite's ability to digest wood. Despite over a century of experimental studies, ecological roles of many of these microbes are unknown, partly because almost none can be cultivated. Many of the protists associate with bacterial symbionts, but hypotheses for their respective roles in nutrient exchange are based on genomes of only two such bacteria. To show how the ecological roles of protists and nutrient transfer with symbiotic bacteria can be elucidated by direct imaging, we combined stable isotope labeling (13C-cellulose) of live termites with analysis of fixed hindgut microbes using correlated scanning electron microscopy, focused ion beam-scanning electron microscopy (FIB-SEM), transmission electron microscopy, and high resolution imaging mass spectrometry (NanoSIMS). We developed methods to prepare whole labeled cells on solid substrates, whole labeled cells milled with a FIB-SEM instrument to reveal cell interiors, and ultramicrotome sections of labeled cells for NanoSIMS imaging of 13C enrichment in protists and associated bacteria. Our results show these methods have the potential to provide direct evidence for nutrient flow and suggest the oxymonad protist Oxymonas dimorpha phagocytoses and enzymatically degrades ingested wood fragments, and may transfer carbon derived from this to its surface bacterial symbionts.

For a few years, the biological effects on ecosystems and the public of the bioaccumulation of radionuclides in situations of chronic exposures have been studied. This work, in keeping with the ENVIRHOM French research program, presents the uranium microdistribution by secondary ion mass spectrometry (SIMS) technique in the renal cortex of rats following chronic exposure to this low level element in the drinking water (40 mg/L) as a function to exposure duration (6, 9, 12, and 18 months). The SIMS mass spectra and 238U+ ion images produced with a SIMS CAMECA 4F-E7 show the kinetic of uranium accumulation in the different structures of the kidney. For the rats contaminated up to 12 months, the radioelement is mainly fixed in the proximal tubules; then after 18 exposure months, uranium is detected in all the segments of the nephron. This work has also shown that ion microscopy is an analytical method to detect trace elements and give elemental cartography at the micrometer scale.

Because the ability to perform some form of chemical microanalysis has become an essential feature for any microscope, it is necessary to investigate what options are available in the new “ORION” helium ion microscope (HIM). The HIM has the ability to visualize local variations in specimen chemistry in both the ion induced secondary electron and the Rutherford backscattered imaging modes, but this provides only limited and qualitative information. Quantitative, elementally specific, microanalysis could be performed in the HIM using secondary electron spectroscopy, Rutherford backscattered ion spectroscopy, or secondary ion mass spectroscopy, but while each of these options has promise, none of them can presently guarantee either reliable element identification or quantitative analysis across the periodic table.

This article discusses the results of transmission electron microscopy (TEM)-based characterization of strontium-doped lead zirconate titanate (PSZT) thin films. The thin films were deposited by radio frequency magnetron sputtering at 300°C on gold-coated silicon substrates, which used a 15 nm titanium adhesion layer between the 150 nm thick gold film and (100) silicon. The TEM analysis was carried out using a combination of high-resolution imaging, energy filtered imaging, energy dispersive X-ray (EDX) analysis, and hollow cone illumination. At the interface between the PSZT films and gold, an amorphous silicon-rich layer (about 4 nm thick) was observed, with the film composition remaining uniform otherwise. The films were found to be polycrystalline with a columnar structure perpendicular to the substrate. Interdiffusion between the bottom metal layers and silicon was observed and was confirmed using secondary ion mass spectrometry. This occurs due to the temperature of deposition (300°C) being close to the eutectic point of gold and silicon (363°C). The diffused regions in silicon were composed primarily of gold (analyzed by EDX) and were bounded by (111) silicon planes, highlighted by the triangular diffused regions observed in the two-dimensional TEM image.

A radioactive particle embedded in a sediment collected from the Irish Sea was examined with spectrometric methods to understand the potential bioavailability of its constituents. Images of the particle surface were acquired in the backscattering mode by scanning electron microscopy. The elemental composition of the particle surface layer was measured using energy dispersive (SEM-EDX) and wavelength dispersive (SEM-WDX) X-ray spectrometers. The investigation showed that the sample consists of a calcite matrix in which uranium is present in the form of separate inclusions. The diameter of U inclusions was less than 10 μm. Synchrotron radiation based X-ray fluorescence in confocal geometry (confocal μ-XRF) was used to determine the spatial distribution of elements in the particle. Three-dimensional reconstructions of the Ca, Cr, Mn, Fe, Zn, Sr, Ba, Pb, and U distributions were performed. The oxidation state of uranium in the different inclusions was determined by synchrotron radiation based X-ray absorption in confocal geometry (confocal μ-XANES). The isotopic composition of uranium was measured by secondary ion mass spectrometry. The results revealed that uranium was depleted in 235U. Pu and other actinides were not detected.

The application of scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS) for characterization of mixed plutonium and uranium particles from nuclear weapons material is presented. The particles originated from the so-called Thule accident in Greenland in 1968. Morphological properties have been studied by SEM and two groups were identified: a “popcorn” structure and a spongy structure. The same technique, coupled with an energy-dispersive X-ray (EDX) spectrometer, showed a heterogeneous composition of Pu and U in the surface layers of the particles. The SIMS depth profiles revealed a varying isotopic composition indicating a heterogeneous mixture of Pu and U in the original nuclear weapons material itself. The depth distributions agree with synchrotron-radiation-based μ-XRF (X-ray fluorescence microprobe) measurements on the particle (Eriksson, M., Wegryzynek, D., Simon, R., & Chinea-Cano, E., in prep.) when a SIMS relative sensitivity factor for Pu to U of 6 is assumed. Different SIMS identified isotopic ratio groups are presented, and the influence of interferences in the Pu and U mass range are estimated. The study found that the materials are a mixture of highly enriched 235U (235U:238U ratio from 0.96 to 1.4) and so-called weapons grade Pu (240Pu:239Pu ratio from 0.028 to 0.059) and confirms earlier work reported in the literature.

Ion microprobe (SIMS) dating shows that three plutonic rock bodies representative of the major, ∼15 000 km2, late tectonic (late-D3), plutonic rock series in the Central Iberian Zone of the Hercynian belt in west-central Iberia have indistinguishable zircon crystallization ages. Ledrada biotite granite and Colmenar cordierite-bearing biotite granite show gradual transitions in field appearance, petrography and chemistry and have statistically indistinguishable weighted average ages of 306.8 ± 1.9(2σ) Ma and 306.5 ± 1.5(2σ) Ma, respectively, which indicates that they originated during a single event involving a heterogeneous magma which notably varied in Al-content. The third rock body, Navahermosa meta-gabbronorite, has a weighted average zircon crystallization age of 305.6 ± 1.4(2σ) Ma, statistically indistinguishable (variance analysis, F-test, α = 0.05) from the granites. Zircon crystals in the gabbronoritic rock are anhedral, skeletal, millimetre-sized and partake in main magmatic textures, whereas the zircon grains in the granites are of more common appearance, much smaller, usually euhedral and enclosed in main magmatic crystals. As gestation times of granitic zircon, the time between zircon crystallization and magmatic intrusion, may be up to 5 Myr, the crystallization age of the gabbronoritic zircon may be the best estimate of the time of emplacement of the magmatic complex. Our study indicates co-existence of basic and silicic magmas in the Hercynian crustal section at c. 306 Ma, suggesting common genetic control. The two granitic rocks carry inherited zircon ranging from c. 1300 to 330 Ma, indicating that pre-Hercynian basement rocks of Proterozoic to Palaeozoic age contributed to the granitic magma.

Ion microprobe (SIMS) dating of zircon from the Miranda do Douro orthogneiss, Central Iberian Zone, Hercynian Iberian belt, defines an Early Ordovician U–Pb age of 496.0 ± 2.6 Ma (95 % conf., MSWD = 1.14) for magmatic zircon crystallization in its granitic protolith. The age contrasts with an earlier, conventional (ID-TIMS) U–Pb zircon age of 618 ± 9(95 % conf.) Ma, now thought to be an artefact of the complex zircon population. Individual SIMS ages for zircon from the rock range from 2700 to 180 Ma and comprise inherited and magmatic zircon, both concordant and common Pb-enriched, and younger, reset ages. The ID-TIMS study seems to have misinterpreted this heterogeneous population as a cogenetic suite consisting of magmatic zircon and its age-reset equivalents produced by recent Pb loss. The 496 ± 3 Ma SIMS age represents the weighted average for 26 magmatic zircon domains located by careful inspection of cathodoluminescence, secondary electron and optical microscopy images of ∼ 700 individual zircon crystals. Inherited zircon is widespread, ranging in age from 2700 to 550 Ma, with age clusters, which are statistically indistinguishable from those known from pre-Hercynian granitic basement material elsewhere in the Central Iberian Zone. Including the present age information, 582 ± 4 Ma (95 % conf., MSWD = 1.02, n = 13) and 619 ± 9 Ma (95 % conf., MSWD = 0.93, n = 7) appear as prevailing inherited zircon age components in basement intrusions in the Central Iberian Zone.

The Svecofennian Domain of the Fennoscandian Shield constitutes a considerable volume of Palaeoproterozoic crustal growth, 2.1–1.86 Ga ago, in between the Archaean craton in the NE and the 1.85–1.65 Ga Transscandinavian Igneous Belt (TIB) in the south and west. The Bergslagen area is a classical ore province located in the southwestern part of the Svecofennian Domain of south-central Sweden. Its northern part is dominated by volcanic and plutonic rocks of a magmatic arc with continental affinity, while the SE part is made up by a sedimentary basin. The Bergslagen area shows a metamorphic zonation from lower to middle amphibolite facies in the north to upper amphibolite facies and locally granulite facies in the south; a small greenschist area exists in the west. Identifying the age spectra of inherited components, magmatic crystallization, as well as metamorphic episodes, provide important constraints on the geodynamic evolution of this centrally located piece of the Shield.

U–Pb zircon SIMS data presented in this paper complement the previous, regionally scattered TIMS data from this area. Magmatic zircons from two felsic metavolcanic rocks and two amphibolites (metagabbros) yield 1888±12, 1892±7 and 1887±5, 1895±5 Ma, respectively; i.e. within the 1.91–1.86 Ga range previously obtained for Early Svecofennian magmatism in Bergslagen. An augen gneiss from southern Bergslagen, assigned to the earliest TIB generation, yield an intrusive age of 1855±6 Ma. Metamorphic monazites from the same rock indicate that deformation and elevated thermal activity prevailed 1.83–1.82 Ga ago (TIMS). Metamorphic zircons in high-grade metasedimentary rocks from the south and west yield ages of 1793±5 and 1804±10 Ma, in accordance with ages for regional peak metamorphism and migmatite formation found elsewhere in the southern Svecofennian province of Sweden. More importantly, a few zircon crystals and overgrowths in rocks from the north indicate an early metamorphic episode at c. 1.87 Ga, indicating that Bergslagen has experienced two major metamorphic events. Detrital and inherited zircons span the range 2.78–1.90 Ga, with an apparent gap at 2.45–2.1 Ga, which further emphasize previous observations of a major juvenile (<2.1 Ga) and a minor Archaean provenance. This, and in particular the 1.94–1.91 Ga crystals present in the c. 1.89 Ga amphibolites, support the suggestion of a former Palaeoproterozoic pre-1.91 Ga crust in the Bergslagen area.

The focus of this review is on trace-element quantitation of microstructures in solids. This review is aimed at the nonspecialist who wants to know how secondary ion mass spectrometry (SIMS) quantitation is achieved. Despite 35 years of SIMS research and applications, SIMS quantitation remains a fundamentally empirical enterprise and is based on standards. The most used standards are “bulk standards”—solids with a homogeneous distribution of a trace element—and ion-implanted solids. The SIMS systematics of bulk standards and ion-implanted solids are reviewed.

Physical, chemical, and isotopic analyses of individual radioactive and other particles in the micron-size range, key tools in environmental research and in nuclear forensics, require the ability to precisely relocate particles of interest (POIs) in the secondary ion mass spectrometer (SIMS) or in another instrument, after having been located, identified, and characterized in the scanning electron microscope (SEM). This article describes the implementation, testing, and evaluation of the triangulation POIs re-location method, based on microscopic reference marks imprinted on or attached to the sample holder, serving as an inherent coordinate system. In SEM-to-SEM and SEM-to-SIMS experiments re-location precision better than 10 μm and 20 μm, respectively, is readily attainable for instruments using standard specimen stages. The method is fast, easy to apply, and facilitates repeated analyses of individual particles in different instruments and laboratories.