Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

Methodology and Application of Hafnium Isotopes in Ilmenite and Rutile by MC‐ICP‐MS

The high abundances of the high field‐strength elements in ilmenite and rutile make these minerals particularly suitable for hafnium isotopic investigations. We present a technique for separating Hf by ion exchange chemistry from high‐TiO₂ (> 40% m/m) minerals to achieve precise Hf isotopic composition analyses by MC (multiple collector)‐ICP‐MS. Following digestion and conversion to chlorides, the first elution column is used to separate iron and the rare earth elements, the second column is designed to separate most of the titanium from Hf, an evaporation step using HClO₄ is then performed to remove any trace of HF in preparation for the third column, which is needed to eliminate any remaining trace of titanium. The modified chemistry helped to improve the yields from < 10 to > 78% as well as the analytical precision of the processed samples (e.g., sample 2033‐A1, ¹⁷⁶Hf/¹⁷⁷Hf = 0.282251 ± 25 before vs. 0.282225 ± 6 after). The technique was tested on a case study in which the Hf isotopic ratios of ilmenite and rutile (analysed prior to the chemistry improvement) were determined and permitted to evaluate that the origin of rutile‐bearing ilmenite deposits is from the same or similar magma than their, respectively, associated Proterozoic anorthosite massifs (Saint‐Urbain and Lac Allard) of the Grenville Province in Québec, Canada.     

Chemical Characterisation of Natural Ilmenite: A Possible New Reference Material

Seven ilmenite (FeTiO₃) megacrysts derived from alnöite pipes (Island of Malaita, Solomon Islands) were characterised for their major and trace element compositions in relation to their potential use as secondary reference materials for in situ microanalysis. Abundances of thirteen trace elements obtained by laser ablation ICP‐MS analyses (using the NIST SRM 610 glass reference material) were compared with those determined by solution‐mode ICP‐MS measurements, and these indicated good agreement for most elements. The accuracy of the LA‐ICP‐MS protocol employed here was also assessed by repeated analysis of MPI‐DING international glass reference materials ML3B‐G and KL2‐G. Several of the Malaitan ilmenite megacrysts exhibited discrepancies between laser ablation and solution‐mode ICP‐MS analyses, primarily attributed to the presence of a titano‐magnetite exsolution phase (at the grain boundaries), which were incorporated solely in the solution‐mode runs. Element abundances obtained by LA‐ICP‐MS for three of the ilmenite megacrysts (CRN63E, CRN63H and CRN63K) investigated here had RSD (2s) values of < 20% and therefore can be considered as working values for reference purposes during routine LA‐ICP‐MS analyses of ilmenite.     

The Design of Re‐usable Carius Tubes for the Determination of Rhenium,Osmium and Platinum‐Group Elements in Geological Samples

The traditional Carius tube technique is cumbersome and requires skilful work to seal the Carius tube, which can be used only once. We describe a modification to the technique that does not require the use of a high‐temperature welding torch to melt the Carius tube to seal it. The newly designed Carius tube consists of a main body with a 3 mm‐thick glass wall, a neck and head with walls 4 mm in thickness, and an efficient screw‐thread stopper. These new features allowed the tube to be used repeatedly. We demonstrate relatively low procedural blanks derived for Re and Os, and platinum‐group elements (PGEs), using the redesigned tube. A temperature of 220 °C could be reached for about 5 ml of HNO₃ for a 47 ml tube and for 32 ml of inverse aqua regia for a 200 ml tube. This digestion technique can be used for routine analysis of Re and PGEs in geological samples.     

矽线石莫来石化的X射线定量分析

本文介绍用X射线粉晶衍射分析方法对夕线石在不同温度的烧制品中的莫来石进行定量分析;指出莫来石和矽线石的(220)峰可作为特征峰,并发现莫来石起始生成和完全莫来石化的温度随原料杂质和粒度因素而变化;认为d(020)=0.383 7nm,d(040)=0.191 7nm是矽线石JCPDS卡片中不曾标定的衍射峰,d(020)=0.3845nm是莫来石不曾标定的衍射峰,它们的强度变化是莫来石化行为特征之一。     

Ni-Co sulphide segregation in the Mamb pyroxenite intrusion, Cameroon

The amphibole metapyroxenite intrusion from Mamb (Cameroon) consists of enstatite, diopside-augite, edenite, and traces of plagioclase, biotite and rutile. It contains notable amounts of sulphides (pyrrhotite, pentlandite, chalcopyrite, pyrite and Co-rich violarite). The sulphide phase segregated during magma crystallization as immiscible droplets (≤ 1 mm) included in growing ferromagnesian minerals or aggregated in the silicate crystal mush to form an interstitial phase. However, observed sulphide assemblages are likely to result from low-T (≤ 300 °C) re-equilibration of high-T monosulphide solid solutions, more particularly during the Pan-African metamorphic event. The Mamb amphibole pyroxenite intrusion is tentatively considered as a potential source for Ni and Co mineralization.     

Numerical simulations of shake-table experiment for dynamic soil-pile-structure interaction in liquefiable soils

A shake-table experiment on pile foundations in liquefi able soils composed of liquefi able sand and overlying soft clay is studied. A three-dimensional(3D) effective stress fi nite element(FE) analysis is employed to simulate the experiment. A recently developed multi-surface elasto-plastic constitutive model and a fully coupled dynamic inelastic FE formulation(u-p) are used to model the liquefaction behavior of the sand. The soil domains are discretized using a solid-fl uid fully coupled(u-p) 20-8 noded brick element. The pile is simulated using beam-column elements. Upon careful calibration, very good agreement is obtained between the computed and the measured dynamic behavior of the ground and the pile. A parametric analysis is also conducted on the model to investigate the effect of pile-pinning, pile diameter, pile stiffness, ground inclination angle, superstructure mass and pile head restraints on the ground improvement. It is found that the pile foundation has a noticeable pinning effect that reduces the lateral soil displacement. It is observed that a larger pile diameter and fi xed pile head restraints contribute to decreasing the lateral pile deformation; however, a higher ground inclination angle tends to increase the lateral pile head displacements and pile stiffness, and superstructure mass seems to effectively infl uence the lateral pile displacements.