Newly developed techniques of electron probe microanalyzer for studying crystal chemistry of minerals

Thesis (Ph. D. in Science)--University of Tsukuba, (B), no. 1893, 2003.1.31Includes bibliographical reference

Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H2O (OH: 0.40 apfu.), while the latter has 1.65 wt% H2O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (Fo> 4sigFo) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca0.83Mn2+ 0.06Fe2+ 0.11)(La0.24Ce0.32Pr0.04Nd0.11Sm0.02Th0.04Ca0.21)(Al0.73Fe3+ 0.19Ti0.08)(Al0.89Fe3+ 0.11)(Fe2+ 0.22Fe3+ 0.62Mg0.16)(SiO4)Si2O7O1.6(OH)0.4, SK100-VAB: (Ca0.81Fe2+ 0.13Mn2+ 0.06)(La0.22Ce0.34Pr0.05Nd0.13Sm0.02Th0.02Ca0.22)(Al0.76Fe3+ 0.19Ti0.05)Al1.00(Fe2+ 0.73Fe3+ 0.17Mg0.10)(Si0.96Al0.04O4)Si2O7O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe2+ to Fe3+, release of H2, and the concomitant replacement of OH− by O2−. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well

Dissakisite-(Ce) chemical composition: some implications for its origins

Euhedral dissakisites from Trimouns dolomite mine, France, is compositionally zoned. Back-scattered electron (BSE) images reveal that each of the described dissakisite crystals has three distinct compositional zones: normal zoned core (Mg-rich), oscillatory zoned middle (Ca–Al-rich) and homogeneous rim (Fe–ΣREE-rich). The latter zone with Fe2+ > Mg corresponds to allanite-(Ce). Dissakisite-(Ce) also displays pronounced zoning in Fe/Mg which may suggest that the temperature of crystallization continuously decreased from core to rim. Despite a systematic increase in Fe/Mg of the dissakisite with an allanite rim, there is no monotonic decrease in the REE zoning: the normal zoned core and homogeneous rim are rich in La, Ce and Pr, but the relatively REE-poor oscillatory zoned middle is relatively abundant in Y, Sm and Gd. Discontinuous variation in REE content of the dissakisite, with the allanite rim may indicate a localized change in either the relative concentration of various ligands or pH of the crystallizing fluid. Observations under the polarizing microscope confirm that the different zones have simultaneous extinction. These chemical and optical observations suggest that epitaxial crystallization of dissakisite, from Trimouns, passes through three formation stages. The ternary Fe2+–Mg2+–(Al + Fe)3+ diagram illustrates that in general dissakisite can be classified into two groups, (Al + Fe)3+-rich and an Mg-rich; dissakisite from Trimouns belongs to the former group. Chondrite-normalized REE patterns of dissakisites from Trimouns are similar to those of allanites formed by hydrothermal fluids. In conclusion, it is clear from the above two geochemical characteristics that dissakisites from Trimouns are of (Al + Fe)3+-type, and were derived from hydrothermal fluids

Crystal chemical significance of chemical zoning in dissakisite-(Ce)

Dissakisites from Trimouns dolomite mine,France, have two kinds of single crystals: chemical-zonedand homogeneous types. Back-scattered electron microprobe(BSE) images of these dissakisites reveal both Ca–Al rich dark zones and Fe-RREE rich bright zones.Crystal structures of three dark and two bright zones in achemical-zoned dissakisite and of a homogeneous zone inunzoned dissakisite were refined to individual R indices(about 3.0–5.0%) based on 1,400 observed [F0[4rF0]reflections measured with MoKa X-radiation using thesingle crystal diffractometer. The differences in brightnessbetween their BSE images arise from those in coupledsubstitutions of the elements occupying A2 and M3 sites.The main reason for these differences is that ten-coordinatedA2 polyhedra and M3 octahedra are directly linkedthrough their shared edge, which creates a great potentialfor making this coupled substitution. This zoning indicatesthat formation of the whole zoned crystal, where eachzone could be grown steadily with its crystallographicaxes mutually parallel to each other, may be identified asautoepitaxy

Giant-Cell Tumor of the Distal Ulna Treated by Wide Resection and Ulnar Support Reconstruction: A Case Report

Giant-cell tumor of bone occurred in the distal end of the ulna is extremely uncommon. A 23-year-old male had a giant-cell tumor occurred in the distal end of the ulna. After wide resection of the distal segment of the ulna including giant-cell tumor, ulnar components of the wrist joint were reconstructed with modified Sauvé-Kapandji procedure using the iliac bone graft, preserving the triangular fibrocartilage complex and ulnar collateral ligament in order to maintain ulnar support of the wrist, and the proximal stump of the resected ulna was stabilized by tenodesis using the extensor carpi ulnaris tendon. One year after operation, the patient's wrist was pain-free and had a full range of motion. Postoperative X-rays showed no abnormal findings including recurrence of the giant-cell tumor and ulnar translation of the entire carpus. The stability of the proximal stump of the distal ulna was also maintained

Intra-Articular Corrective Osteotomy for Distal Radial Intra-Articular Malunion Using Patient-Matched Instruments: A Prospective, Multicenter, Open-Label, Single-Arm Trial

Oka K., Miyamura S., Shiode R., et al. Intra-Articular Corrective Osteotomy for Distal Radial Intra-Articular Malunion Using Patient-Matched Instruments: A Prospective, Multicenter, Open-Label, Single-Arm Trial. JBJS Open Access 9, e24.00026 (2024); https://doi.org/10.2106/JBJS.OA.24.00026.Background:Corrective osteotomy for intra-articular malunion is a challenging procedure. However, recent advancements, including patient-matched instruments created on the basis of preoperative computer simulation, enable accurate intra-articular correction. We hypothesized that intra-articular corrective osteotomy using patient-matched instruments for the treatment of distal radial intra-articular malunion would reduce intra-articular deformity and restore wrist function at 12 months of follow-up.Methods:This prospective study included 12 patients with distal radial intra-articular malunion who underwent intra-articular corrective osteotomy external to the joint using patient-matched instruments. The primary end point was the maximum step-off on the articular surface of the distal radius, measured with use of computed tomography (CT), with an expected postoperative value of ≤1.5 mm. The secondary end points included the gap of the articular surface; range of motion; grip strength; pain evaluated using a visual analog scale (VAS); patient satisfaction; Disabilities of the Arm, Shoulder and Hand (DASH) score; and Patient-Rated Wrist Evaluation (PRWE) score. A mean postoperative step-off of ≤1.5 mm for the primary end point was assessed with use of the 1-sample t test. The secondary end points were assessed with use of the Dunnett multiple comparison test.Results:The average step-off significantly improved from 3.75 ± 1.04 mm preoperatively to 0.51 ± 0.40 mm at the 52-week postoperative follow-up and was maintained within 1.5 mm. The average wrist and forearm range of motion, VAS score, grip strength, DASH score, and PRWE score significantly improved. Eleven patients were either very satisfied or satisfied with their outcomes.Conclusions:The use of patient-matched instruments could contribute to improving postoperative outcomes of intra-articular corrective osteotomy procedures involving the distal radius.Level of Evidence:Therapeutic Level IV. See Instructions for Authors for a complete description of levels of evidence

A nationwide, multi-center, retrospective study of symptomatic small bowel stricture in patients with Crohn\u27s disease.

BACKGROUND:Small bowel stricture is one of the most common complications in patients with Crohn\u27s disease (CD). Endoscopic balloon dilatation (EBD) is a minimally invasive treatment intended to avoid surgery; however, whether EBD prevents subsequent surgery remains unclear. We aimed to reveal the factors contributing to surgery in patients with small bowel stricture and the factors associated with subsequent surgery after initial EBD.METHODS:Data were retrospectively collected from surgically untreated CD patients who developed symptomatic small bowel stricture after 2008 when the use of balloon-assisted enteroscopy and maintenance therapy with anti-tumor necrosis factor (TNF) became available.RESULTS:A total of 305 cases from 32 tertiary referral centers were enrolled. Cumulative surgery-free survival was 74.0% at 1 year, 54.4% at 5 years, and 44.3% at 10 years. The factors associated with avoiding surgery were non-stricturing, non-penetrating disease at onset, mild severity of symptoms, successful EBD, stricture length < 2 cm, and immunomodulator or anti-TNF added after onset of obstructive symptoms. In 95 cases with successful initial EBD, longer EBD interval was associated with lower risk of surgery. Receiver operating characteristic analysis revealed that an EBD interval of ≤ 446 days predicted subsequent surgery, and the proportion of smokers was significantly high in patients who required frequent dilatation.CONCLUSIONS:In CD patients with symptomatic small bowel stricture, addition of immunomodulator or anti-TNF and smoking cessation may improve the outcome of symptomatic small bowel stricture, by avoiding frequent EBD and subsequent surgery after initial EBD

A Classification of Several Yamato-74 Chondrites

Six Yamato-74 chondritic meteorites have been classified, based on iron contents of olivines and orthopyroxenes in their small fragments. The results are as follows : Yamato-74193,-74498 and -74507 are H4-chondrites, Yamato-74367 and -74603 are L4-chondrites, and Yamato-74454 is L5-chondrite

Origin and Evolution of Condrules Based on Na/Al-Dispersion and -Convergence in Yamato-74 Ordinary Chondrites

Na/Al convergence has been observed in groundmass of chondrules and matrix from seven Yamato-74 (H, L, 4-5) chondrites. On the other hand, Na/Al dispersion has prevailed in groundmass of chondrules and matrix from Yamato-74191 (L3) chondrite. The results suggest that : (1) Primordial liquid droplets as precursors of the chondrules might be derived from a rapidly cooling solar nebula by fractional condensation. (2) The hot liquid droplets thus formed might be cooled instantaneously by radiation loss in the cooling nebula. (3) The chondrules as quenched products might be subjected to mutual collision during accumulation in the cold nebula. (4) Planetesimals accumulated by the chondrules might be transferred from the place of birth to an unknown hot region in the proto solar nebula