Louis J. Cabri

Micro-PIXE as a complement to electron probe microanalysis in mineralogy☆

Abstract Standardization methods and limits of detection for the analogous techniques of micro-PIXE and electron-probe microanalysis (EPMA) are compared in the context of mineralogical applications, specifically in the analysis of sulfide and oxide minerals. Micro-PIXE benefits by adopting and adapting techniques from EPMA and the two techniques are often deployed in tandem to provide a full characterization spanning major, minor and trace elements. Various examples are given of work in progress.

Skaergaardite, PdCu, a new platinum-group intermetallic mineral from the Skaergaard intrusion, Greenland

Abstract Skaergaardite, PdCu, is a new mineral discovered in the Skaergaard intrusion, Kangerdlugssuaq area, East Greenland. It occurs in a tholeitiic gabbro associated with plagioclase, clinopyroxene, orthopyroxene, ilmenite, titanian magnetite, fayalite and accessory chlorite-group minerals, ferrosapo- nite, a member of the annite-phlogopite series, hornblende, actinolite, epidote, calcite, ankerite, apatite and baddeleyite. The mineral is found in composite microglobules composed of bomite, chalcocite, digenite, chalcopyrite, with rare cobalt pentlandite, cobaltoan pentlandite, sphalerite, keithconnite, vasilite, zvyagintsevite, (Cu5Pd5Au) and Pt-Fe-Cu-Pd alloys, unnamed PdCu3, (Pd,Cu,Sn), Au3Cu and PdAuCu. Skaergaardite occurs as droplets, equant grains with rounded outlines, subhedral to euhedral crystals and as irregular grains that vary in size from 2 to 75 pm, averaging 22 pm. It is steel grey with a bronze tint, has a black streak, a metallic lustre and is sectile. Neither cleavage nor fracture was observed. The mineral has a micro-indentation hardness of VHN25 = 257. It is isotropic, non-pleochroic and exhibits neither discernible internal reflections nor evidence of twinning. Skaergaardite varies from bright creamy white (associated with bomite and chalcopyrite) to bright white (associated with digenite and chalcocite). Reflectance values in air (and in oil) are: 58.65 (47.4) at 470 nm, 62.6 (51.1) at 546 nm, 64.1 (52.8) at 589 nm and 65.25 (53.95) at 650 nm. The average of 311 electron-microprobe analyses gives: Pd 58.94, Pt 1.12, Au 2.23, Cu 29.84, Fe 3.85, Zn 1.46, Sn 1.08, Te 0.28 and Pb 0.39, total 99.19 wt.%, corresponding to (Pd0.967Au0.020Pt0.010)∑0.997(Cu0.820Fe0.120Zn0.039Sn0.016Te0.004Pb0.003)∑1.002. The mineral is cubic, space group Pm3m, a = 3.0014(2) Å, V = 27.0378 Å3, Z = 1. Dcalc is 10.64 g/cm3. The six strongest lines in the X-ray powder-diffraction pattern [d in Å(I)(hkl)] are: 2.122(100)(110), 1.5000(20)(200), 1.2254(50)(211), 0.9491(20)(310), 0.8666(10)(222), 0.8021(70)(321). The mineral has the CsCl-type structure. It is believed to be isostructural with wairauite (CoFe), synthetic CuZn (β-brass) and is structurally related to hongshiite (PtCu). Skaergaardite developed from a disordered Pd-Cu-rich metal alloy melt that had exsolved from an earlier Cu-(Fe) sulphide melt. Ordering of Pd and Cu (beginning at T ≈ 600°C) results in development of the CsCl structure from a disordered face-centred cubic structure.

Origin of placer laurite from Borneo: Se and As contents, and S isotopic compositions

Abstract We examined grains of the platinum-group mineral, laurite (RuS2), from the type locality, Pontyn River, Tanah Laut, Borneo, and from the Tambanio River, southeast Borneo. The grains show a variety of morphologies, including euhedral grains with conchoidal fractures and pits, and spherical grains with no crystal faces, probably because of abrasion. Inclusions are rare, but one grain contains Ca-Al amphibole inclusions, and another contains an inclusion of chalcopyrite+bornite+pentlandite+heazlewoodite (Ni3S2) that is considered to have formed by a two-stage process of exsolution and crystallization from a once homogeneous Fe-Cu-Ni sulphide melt. All grains examined are solid solutions of Ru and Os with Ir (2.71−11.76 wt.%) and Pd (0.31−0.66 wt.%). Their compositions are similar to laurite from ophiolitic rocks. The compositions show broad negative correlations between Os and Ir, between As and Ir, and between As (0.4−0.74 wt.%) and Se (140 to 240 ppm). Laurite with higher Os contains more Se and less Ir and As. The negative correlations between Se and As may be attributed to their occupancy of the S site, but the compositional variations of Os, Ir and As probably reflect the compositional variation of rocks where the crystals grew. Ratios of S/Se in laurite show a narrow spread from 1380 to 2300, which are similar to ratios for sulphides from the refractory sub-arc mantle. Sulphur isotopic compositions of laurite are independent of chemical compositions and morphologies and are similar to the chondritic value of 0‰. The data suggest that S in laurite has not undergone redox changes and originated from the refractory mantle. The data support the formation of laurite in the residual mantle or in a magma generated from such a refractory mantle, followed by erosion after the obduction of the host ultramafic rocks.

Comparison of in-situ gold analyses in arsenian pyrite

Abstract In-situ analyses of Au in arsenian pyrite, a Au-carrier common in certain ores refractory to direct cyanidation, are feasible by proton and ion microprobe. These in-situ microbeam analysis techniques provide a better geochemical understanding of the distribution of Au in ore than traditional bulk chemical analyses. The practical minimum detection level (MDL) by particle induced X-ray excitation (PIXE) or proton microprobe (Micro-PIXE) is 21–26 ppmw for a beam density of 22–24 pA/μm 2 . A lower MDL of ∼400 ppbw was obtained by secondary ion mass spectrometry (SIMS) or ion microprobe. Results of analysis of the same grains by both methods are not readily comparable because of the inhomogeneous distribution of Au in arsenian pyrite and the different volumes analyzed (∼5000 μm 3 for PIXE vs ∼2400 μm 3 for SIMS). In addition, the geometry of the volume analyzed by each technique is different: a parallelepiped by Micro-PIXE and a thin disc by SIMS.

Osmium isotope ratios of PGM grains associated with the Freetown Layered Complex, Sierra Leone, and their origin

Osmium isotope ratios for two types of platinum group mineral (PGM) nuggets of eluvial (residual) origin, associated with the Freetown Layered Gabbro Complex, were determined in-situ using an ion microprobe. The values for erlichmanite nuggets are ≈1.08. Those for PGM inclusions in Pt−Fe alloy nuggets are higher, ranging from 1.2 to 2.1. Ratios of187Os/186Os vary between the nuggets, but they are consistent within individual nuggest. The data suggest early formation of the erlichmanite nuggets, prior to a postulated substantial contribution of crustal Os. The Pt−Fe alloy nuggets, on the other hand, were formed later in a residual melt which was contaminated by crustal Os due to the assimilation (<10%) or the gaseous/fluid transport of Os from Archaean host rocks into the magma. The lack of systematic mineralogical and chemical changes of the Complex and extensive granulitization in the adjacent host rocks and xenoliths may favor the latter process.The lack of high187Os/186Os ratios, consistent187Os/186Os values within individual nuggets and their textures and mineralogy suggest that the studied PGM nuggets were not formed during lateritization or in low-temperature depositional environments.

Naldrettite, Pd2Sb, a new intermetallic mineral from the Mesamax Northwest deposit, Ungava region, Québec, Canada

Abstract Naldrettite, Pd2Sb, is a new intermetallic mineral discovered in the Mesamax Northwest deposit, Cape Smith fold belt, Ungava region, northern Québec. It is associated with monoclinic pyrrhotite, pentlandite, chalcopyrite, galena, sphalerite, cobaltite, clinochlore, magnetite, sudburyite (PdSb), electrum and altaite. Other rarer associated minerals include a second new mineral (ungavaite, Pd4Sb3), sperrylite (PtAs2), michenerite (PdBiTe), petzite (Ag3AuTe4) and hessite (Ag2Te). Naldrettite occurs as anhedral grains, which are commonly attached or moulded to sulphide minerals, and also associated with clinochlore. Grains of naldrettite vary in size (equivalent circle diameter) from ~10 to 239 μm, with an average of 74.4 μm (n = 632). Cleavage was not observed and fracture is irregular. The mineral has a mean micro-indentation hardness of 393 kg/mm2. It is distinctly anisotropic, non- pleochroic, has weak bireflectance, and does not exhibit discernible internal reflections. Some grains display evidence of strain-induced polysynthetic twinning. Naldrettite appears bright creamy white in association with pentlandite, pyrrhotite, clinochlore and chalcopyrite. Reflectance values in air (and in oil) for R1 and R2 are: 49.0, 50.9 (35.9, 37.6) at 470 nm, 53.2, 55.1 (40.3, 42.1) at 546 nm, 55.4, 57.5 (42.5, 44.3) at 589 nm and 58.5, 60.1 (45.4, 47.2) at 650 nm. The average of 69 electron-microprobe analyses on 19 particles gives: Pd 63.49, Fe 0.11, Sb 35.75, As 0.31, and S 0.02, total 99.68 wt.%, corresponding to (Pd1.995Fe0.007)2.002(Sb0.982As0.014S0.002)0.998. The mineral is orthorhombic, space group Cmc21, a 3.3906(1), b 17.5551(5), c 6.957(2) Å , V 414.097(3) Å3, Z = 8. Dcalc is 10.694(1) g/cm3. The six strongest lines in the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 2.2454(100)(132), 2.0567(52)(043), 2.0009(40)(152), 1.2842(42)(115), 1.2122(50)(204) and 0.8584(56)(1.17.4).

Calibration of micro-PIXE analysis of sulfide minerals

Abstract Two different standardization methods have been used in micro-PIXE analysis of several hundred sulfide mineral specimens. Their advantages and disadvantages are discussed and the compatibility of the two sets of results is investigated.

Palladosilicide, Pd2Si, a new mineral from the Kapalagulu Intrusion, Western Tanzania and the Bushveld Complex, South Africa

Abstract Palladosilicide, Pd2Si, is a new mineral (IMA 2014-080) discovered in chromite-rich samples from the Kapalagulu intrusion, western Tanzania (30°03ʹ51ʺE 5°53ʹ16ʺS and 30°05ʹ37ʺE 5°54ʹ26ʺS) and from the UG-2 chromitite, Bushveld complex, South Africa. A total of 13 grains of palladosilicide, ranging in size from 0.7 to 39.1 μm (equivalent circle diameters), were found. Synthetic Pd2Si is hexagonal, space group P6̅2m, with a = 6.496(5), c = 3.433(4) Å, V = 125.5(1) Å3, c:a = 0.529 with Z = 3. The strongest lines calculated from the powder pattern (Anderko and Schubert, 1953) are [d in Å (I) (hkl)] 2.3658 100 (111); 2.1263 37 (120); 2.1808 34 (021); 3.240 20 (110); 1.8752 19 (030); 1.7265 12 (002); 1.3403 11 (122); 1.2089 10 (231). The calculated density for three analyses varies from 9.562 to 9.753 g cm-3. Palladosilicide is considered to be equivalent to synthetic Pd2Si based on results from electron backscattered diffraction analyses. Reflectance data in air for the four Commission on Ore Mineralogy wavelengths are [λ nm, R1 (%) R2 (%)] 470 49.6 52.7; 546 51.2 53.8; 589 51.6 53.7; 650 51.7 53.3 and the mineral is bright creamy white against chromite, weakly bireflectant and displays no discernible pleochroism or twinning. It is weakly anisotropic, has weak extinction and rotation tints in shades of blue and olive green. Electron probe microanalyses of palladosilicide yield a simplified formula of Pd2Si.