Secondary Alteration Phases Research Articles

Shumwayite, [(UO2)(SO4)(H2O)2]2·H2O, a new uranyl sulfate mineral from Red Canyon, San Juan County, Utah, USA

AbstractThe new mineral shumwayite (IMA2015-058), [(UO2)(SO4)(H2O)2]2·H2O, was found in the Green Lizard and Giveaway-Simplot mines, White Canyon district, San Juan County, Utah, USA, where it occurs as a secondary alteration phase. At the Green Lizard mine, it is found in association with calcite, gypsum, plášilite, pyrite, rozenite and sulfur; at the Giveaway-Simplot mine, shumwayite is associated with rhomboclase and römerite. The mineral occurs as pale greenish-yellow monoclinic prisms, elongated on [100], up to ∼0.3 mm long and commonly in subparallel to random intergrowths. The mineral is transparent with a vitreous lustre and has a white streak. It fluoresces bright greenish white under both longwave and shortwave ultraviolet radiation. The Mohs hardness is ∼2. Crystals are brittle with perfect {011} cleavage and irregular fracture. The mineral is slightly deliquescent and is easily soluble in room temperature H2O. The calculated density is 3.844 g cm–3. Optically, shumwayite is biaxial (+/–), with α = 1.581(1), β= 1.588(1), γ = 1.595(1) (measured in white light). The measured 2Vxbased on extinction data collected on a spindle stage is 89.8(8)°; the calculated 2Vxis 89.6°. Dispersion is strong, but the sense is not defined because the optic sign is ambiguous. No pleochroism was observed. The optical orientation isX=b,Y=c,Z=a. Energy-dispersive spectrometer analyses (with H2O based on the crystal structure) yielded the empirical formula U2.01S1.99O12.00·5H2O.Shumwayite is monoclinic,P21/c,a= 6.74747(15),b= 12.5026(3),c= 16.9032(12) Å, β = 90.919(6)°,V= 1425.79(11) Å3andZ= 4. The crystal structure (R1= 1.88% for 2936F> 4σF) contains UO7pentagonal bipyramids and SO4tetrahedra that link by corner-sharing to form [(UO2)(SO4)(H2O)2] chains along [100]. The chains and isolated H2O groups between them are linked together only by hydrogen bonds. The mineral is named in honour of the Shumway family, whose members account for the discovery and mining of hundreds of uranium deposits on the Colorado Plateau, including the Green Lizard mine.

Chongite, Ca3Mg2(AsO4)2(AsO3OH)2·4H2O, a new arsenate member of the hureaulite group from the Torrecillas mine, Iquique Province, Chile

AbstractThe new mineral chongite (IMA2015–039), Ca3Mg2(AsO4)2(AsO3OH)2.4H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with native arsenic, arsenolite, gajardoite, talmessite and torrecillasite. Chongite occurs as prismatic crystals up to ∼1 mm long grouped in tightly intergrown radial aggregates up to 2 mm in diameter. Crystals are transparent, with vitreous lustre and white streak. The Mohs hardness is∼3½,tenacity is brittle and fracture is conchoidal. Cleavage is good on ﹛100﹜. The measured density is 3.09(2) g/cm3and the calculated density is 3.087 g/cm3. Optically, chongite is biaxial (-) with α = 1.612(1), β= 1.626(1), γ= 1.635(1) and 2V = 76.9(1)° (measured in white light). Dispersion isr < v,distinct. The optical orientation isX= b;Z^a =27° in obtuse angle β. The mineral is slowly soluble in dilute HCl at room temperature. The empirical formula, determined from electron-microprobe analyses, is (Ca2.90Mg1.93Mn0.14)Σ4.97As4O20H10.07. Chongite is monoclinic,die, a =18.5879(6),b =9.3660(3),c =9.9622(7) Å, β = 96.916(7)°,V=1721.75(14) Å3and Z=4. The eight strongest powder X-ray diffraction lines are[dobsÅ(I)(hkl)]: 8.35(29)(110), 4.644(62) (3ˉ11,020,400,2̄02), 4.396(26)(311), 3.372(62)(022,312,5̄11), 3.275(100)(420,22ˉ2,421), 3.113(57)(222), 2.384(30)(711,530,7̄12) and 1.7990(22)(9̄13,334,5̄34). The structure determination(R1= 1.56% for 1849 Fo> 4σFreflections) confirms that chongite is a member of the hureaulite group.

Gajardoite, KCa0.5As3+4O6Cl2·5H2O, a new mineral related to lucabindiite and torrecillasite from the Torrecillas mine, Iquique Province, Chile

AbstractThe new mineral gajardoite (IMA2015-040), KCa0.5As3+4O6Cl2·5H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with native arsenic, arsenolite,chongite, talmessite and torrecillasite. Gajardoite occurs as hexagonal plates up to ∼100 μm in diameter and 5 μm thick, in rosette-like subparallel intergrowths. Crystals are transparent, with vitreous lustre and white streak. The Mohs hardness is ∼1½, tenacity is brittleand fracture is irregular. Cleavage is perfect on {001}. The measured density is 2.64 g/cm3 and the calculated density is 2.676 g/cm3. Optically, gajardoite is uniaxial (–) with ω = 1.780(3) and ε = 1.570(5) (measured in white light). The mineral is very slowly soluble in H2O and slowly soluble in dilute HCl at room temperature. The empirical formula, determined from electron-microprobe analyses, is (K0.77Ca0.71Na0.05Mg0.05)∑1.58As4O11Cl1.96H9.62.Gajardoite is hexagonal, P6/mmm, a = 5.2558(8), c = 15.9666(18) Å, V = 381.96(13) Å3 and Z = 1. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 16.00(100)(001), 5.31(48)(003),3.466 (31)(103), 3.013(44)(104), 2.624(51)(006,110,111), 2.353(36)(113), 1.8647(21)(116,205) and 1.4605(17) (119,303,216). The structure, refined to R1 = 3.49% for 169 Fo > 4σF reflections, contains two types of layers. One layer of formulaKAs3+4O6Cl2 consists of two neutral As2O3 sheets, between which are K+ cations and on the outside of which are Cl– anions. This layer is topologically identical to a slice of the lucabindiite structureand similar to a slice of the torrecillasite structure. The second layer consists of an edge-sharing sheet of Ca(H2O)6 trigonal pyramids with isolated H2O groups centred in the hexagonal cavities in the sheet.

Geschieberite, K2(UO2)(SO4)2(H2O)2, a new uranyl sulfate mineral from Jáchymov

AbstractThe new mineral geschieberite (IMA2014-006), K2(UO2)(SO4)2(H2O)2, was found in the Svornost mine, Jáchymov, Czech Republic, where it occurs as a secondary alteration phase after uraninite in association with adolfpateraite and gypsum. Geschieberite forms crystalline aggregates of bright green colour (when thick) composed of multiply intergrown prismatic crystals elongated on [001] typically reaching 0.1–0.2 mm across; observable forms are {010} and {001}. Crystals are translucent to transparent with a vitreous lustre. The mineral is brittle, with perfect cleavage on {100} and an uneven fracture. It has a greenish-white streak and a probable Mohs hardness of ∼2. The mineral is slightly soluble in cold H2O. The calculated density is 3.259 g cm–3. The mineral exhibits strong yellowish-green fluorescence under both shortwave and longwave UV radiation. Optically, geschieberite is biaxial (–), with β = 1.596(2) and γ = 1.634(4) (measured at 590 nm), with X = a. Electron-microprobe analyses provided Na2O 0.23, K2O 14.29, MgO 2.05, CaO 0.06, UO349.51, SO327.74, H2O 6.36 (structure), total 100.24 wt.%, yielding the empirical formula (K1.72Mg0.29Na0.04Ca0.01)Σ2.06(U0.98O2)(S0.98O4)2(H2O)2based on 12 O atoms per formula unit. The Raman spectrum is dominated by the symmetric stretching vibrations of UO22+, SO42–and weaker O–H stretching vibrations. Geschieberite is orthorhombic,Pna21, with a = 13.7778(3), b = 7.2709(4), c = 11.5488(2) Å, V = 1156.92(7) Å3, Z = 4. The eight strongest powder X-ray diffraction lines are [dobsin Å(hkl) Irel]: 6.882 (200) 100, 5.622 (111) 53, 4.589 (211) 12, 4.428 (202) 16, 3.681 (311) 18, 3.403 (013) 12, 3.304 (401,1̄13) 15 and 3.006 (122) 17. The structure, refined to R = 0.028 for 1882 I > 3σ(I) reflections, contains [(UO2)(SO4)2(H2O)]2–sheets that are based on the protasite anion topology. Sheets are stacked perpendicular to a. Potassium atoms and one H2O molecule are located between these sheets, providing an interlayer linkage. The remaining H2O molecule is localized within the structural unit, at the free vertex of the uranyl pentagonal bipyramid; this vertex does not link to sulfate tetrahedra. The mineral is named for one of the most important ore veins in Jáchymov – the Geschieber vein.

Canutite, NaMn3[AsO4][AsO3(OH)]2, a new protonated alluaudite-group mineral from the Torrecillas mine, Iquique Province, Chile

AbstractThe new mineral canutite (IMA2013-070), NaMn3[AsO4][AsO3(OH)]2, was found at two different locations at the Torrecillas mine, Salar Grande, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, halite, lavendulan, magnesiokoritnigite, pyrite, quartz and scorodite. Canutite is reddish brown in colour. It forms as prisms elongated on [20] and exhibiting the forms {010}, {100}, {10}, {201} and {102}, or as tablets flattened on {102} and exhibiting the forms {102} and {110}. Crystals are transparent with a vitreous lustre. The mineral has a pale tan streak, Mohs hardness of 2½, brittle tenacity, splintery fracture and two perfect cleavages, on {010} and {101}. The calculated density is 4.112 g cm−3. Optically, canutite is biaxial (+) with α = 1.712(3), β = 1.725(3) and γ = 1.756(3) (measured in white light). The measured 2V is 65.6(4)°, the dispersion is r < v (slight), the optical orientation is Z = b; X ^ a = 18° in obtuse β and pleochroism is imperceptible. The mineral is slowly soluble in cold, dilute HCl. The empirical formula (for tabular crystals from near the mineshaft), determined from electron - microprobe analyses, is (Na1.05Mn2.64Mg0.34Cu0.14Co0.03)∑4.20As3O12H1.62. Canutite is monoclinic, C2/c, a = 12.3282(4), b = 12.6039(5), c = 6.8814(5) Å, β = 113.480(8)°, V = 980.72(10) Å3 and Z = 4. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 6.33(34)(020), 4.12(26)(21), 3.608(29)(310,31), 3.296(57)(12), 3.150(28)(002,131), 2.819(42)(400,041,330), 2.740(100)(240,02,112) and 1.5364(31)(multiple). The structure, refined to R1 = 2.33% for 1089 Fo > 4σF reflections, shows canutite to be isostructural with protonated members of the alluaudite group.

Torrecillasite, Na(As,Sb)43+O6Cl, a new mineral from the Torrecillas mine, Iquique Province, Chile: description and crystal structure

AbstractThe new mineral torrecillasite (IMA2013-112), Na(As,Sb)43+O6Cl, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, cinnabar, gypsum, halite, lavendulan, magnesiokoritnigite, marcasite, quartz, pyrite, scorodite, wendwilsonite and other potentially new As-bearing minerals. Torrecillasite occurs as thin colourless prisms up to 0.4 mm long in jack-straw aggregates, as very thin fibres in puff balls and as massive intergrowths of needles. Prisms are elongated on [100] with diamond-shaped cross-section and irregular terminations. Crystals are transparent, with adamantine lustre and white streak. The Mohs hardness is 2½, tenacity is brittle and fracture is irregular. Cleavage on (001) is likely. The calculated density is 4.056 g cm−3. Optically, torrecillasite is biaxial (−) with α = 1.800(5), β = 1.96(1), γ = 2.03(calc.) (measured in white light). The measured 2V is 62.1(5)°, no dispersion or pleochroism were observed, the optical orientation isX=c,Y=b,Z=a. The mineral is very slowly soluble in H2O, slowly soluble in dilute HCl and rapidly soluble in concentrated HCl. The empirical formula, determined from electron-microprobe analyses, is (Na1.03Mg0.02)∑1.05(As3.39Sb0.62)∑4.01O6.07Cl0.93. Torrecillasite is orthorhombic,Pmcn, a= 5.2580(9),b= 8.0620(13),c= 18.654(3) Å,V= 790.7(2) Å3andZ= 4. The eight strongest X-ray powder diffraction lines are [dobsÅ(I)(hkl)]: 4.298(33)(111), 4.031(78)(014,020), 3.035(100)(024,122), 2.853(39)(115,123), 2.642(84)(124,200), 2.426(34)(125), 1.8963(32)(225) and 1.8026(29)(0·1·10,233). The structure, refined toR1= 4.06% for 814Fo>4σFreflections, contains a neutral, wavy As2O3layer parallel to (001) consisting of As3+O3pyramids that share O atoms to form six-membered rings. Successive layers are flipped relative to one another and successive interlayer regions contain alternately either Na or Cl atoms. Torrecillasite is isostructural with synthetic orthorhombic NaAs4O6Br.

Belakovskiite, Na7(UO2)(SO4)4(SO3OH)(H2O)3, a new uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah, USA

AbstractThe new mineral belakovskiite (IMA2013-075), Na7(UO2)(SO4)4(SO3OH)(H2O)3, was found in the Blue Lizard mine, Red Canyon, White Canyon district, San Juan County, Utah, USA, where it occurs as a secondary alteration phase in association with blödite, ferrinatrite, kröhnkite, meisserite and metavoltine. Crystals of belakovskiite are very pale yellowish-green hair-like fibres up to 2 mm long and usually no more than a few mm in diameter. The fibres are elongated on [100] and slightly flattened on {021}. Crystals are transparent with a vitreous lustre. The mineral has a white streak and a probable Mohs hardness of ∼2. Fibres are flexible and elastic, with brittle failure and irregular fracture. No cleavage was observed. The mineral is readily soluble in cold H2O. The calculated density is 2.953 g cm−3. Optically, belakovskiite is biaxial (+) with α = 1.500(1), β = 1.511(1) and γ = 1.523(1) (measured in white light). The measured 2V is 87.1(6)° and the calculated 2V is 88°. The mineral is non-pleochroic. The partially determined optical orientation is X ≈ a. Electron-microprobe analysis provided Na2O 21.67, UO3 30.48, SO3 40.86, H2O 6.45 (structure), total 99.46 wt.% yielding the empirical formula Na6.83(U1.04O2)(SO4)4(S0.99O3OH)(H2O)3 based on 25 O a.p.f.u. Belakovskiite is triclinic, P, with a = 5.4581(3), b = 11.3288(6), c = 18.4163(13) Å, α = 104.786(7)°, β = 90.092(6)°, γ = 96.767(7)°, V = 1092.76(11) Å3 and Z = 2. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 8.96(35)(002), 8.46(29)(011), 5.19(100)(01,101,10), 4.66(58)(013,02,0,110), 3.568(37)(120,023,005,03), 3.057(59)(06,15,31), 2.930(27)(multiple) and 1.8320(29)(multiple). The structure, refined to R1 = 5.39% for 3163 Fo > 4σF reflections, contains [(UO2)(SO4)4(H2O)]6− polyhedral clusters connected via an extensive network of Na−O bonds and H bonds involving eight Na sites, three other H2O sites and an SO3OH (hydrosulfate) group. The 3-D framework, thus defined, is unique among known uranyl sulfate structures. The mineral is named for Dmitry Ilych Belakovskiy, a prominent Russian mineralogist and Curator of the Fersman Mineralogical Museum.

Research reactor fuel element corrosion under repository relevant conditions: separation, identification, and quantification of secondary alteration phases of UAl x -Al in MgCl2-rich brine

Abstract The corrosion of the UAl x -Al research reactor fuel type in synthetic MgCl2-rich brine (static batch-type experiments) was investigated with respect to the long-term safety of directly disposed research reactor fuel elements in salt formations. During corrosion, crystalline secondary phases were formed, which may serve as a barrier against radionuclide migration. For an optimized identification and quantification of the secondary phases using X-ray diffraction, a sample treatment to separate and enrich the secondary phases is necessary. A grain size fractionation was carried out in iso-propanol. A chemical composition and phase characterization of the secondary phases was accomplished. The results of the chemical investigations reveal that only traces of Al and U were dissolved. The separation and enrichment of secondary phases were carried out reproducible and successfully. Due to the phase characterization by scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray diffraction the following secondary phases were unambiguously identified: Mg-Al-Cl layered double hydroxide, lesukite, Fe layered double hydroxide (green rust), lawrencite, Fe (elemental), and traces of uncorroded fuel (UAl4). The quantitative analysis showed that LDH compounds and lesukite are the major crystalline phases. All other observed compounds were only present in trace amounts, i.e. constituting accessories. The Rietveld analysis also revealed the high content of amorphous phases of approximately 30%, which are expected to include the uranium as U(OH)4.

Transmission electron microscope analyses of alteration phases in martian meteorite MIL 090032

The nakhlite group of martian meteorites found in the Antarctic contain varying abundances of both martian and terrestrial secondary alteration phases. The aim of this study was to use transmission electron microscopy (TEM) to compare martian and terrestrial alteration embodied within a single nakhlite martian meteorite find – MIL 090032. Martian alteration veins in MIL 090032 are composed of poorly ordered Fe-smectite phyllosilicate. This poorly-ordered smectite appears to be equivalent to the nanocrystalline phyllosilicate/hydrated amorphous gel phase previously described in the martian alteration veins of other nakhlites. Chemical differences in this nanocrystalline phyllosilicate between different nakhlites imply localised alteration, which occurred close to the martian surface in MIL 090032. Both structurally and compositionally the nakhlite nanocrystalline phyllosilicate shows similarities to the amorphous/poorly ordered phase recently discovered in martian soil by the Mars Curiosity Rover at Rocknest, Gale Crater.Terrestrially derived alteration phases in MIL 090032 include jarosite and gypsum, amorphous silicates, and Fe-oxides and hydroxides. Similarities between the mineralogy and chemistry of the MIL 090032 terrestrial and martian alteration phases suggest the alteration conditions on Mars were similar to those in the Antarctic. At both sites a small amount of fluid at low temperatures infiltrated the rock and became acidic as a result of the conversion of Fe2+ to Fe3+ under oxidising conditions.

Magnesiokoritnigite, Mg(AsO3OH)·H2O, from the Torrecillas mine, Iquique Province, Chile: the Mg-analogue of koritnigite

AbstractThe new mineral magnesiokoritnigite (IMA 2013-049), ideally Mg(AsO3OH)·H2O, was found at the Torrecillas mine, Salar Grande, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, chudobaite, halite, lavendulan, quartz and scorodite. Crystals of magnesiokoritnigite are colourless to pale-pink, thin to thick laths up to 2 mm long. Laths are elongated on [001], flattened on {010} and exhibit the forms {010}, {110}, {10}, {101}, {031} and {01}. The crystals also occur in dense deep-pink intergrowths. Crystals are transparent with a vitreous lustre. The mineral has a white streak, Mohs hardness of ∼3, brittle tenacity, conchoidal fracture and one perfect cleavage on {101}. The measured and calculated densities are 2.95(3) and 2.935 g cm– 3, respectively. Optically, magnesiokoritnigite is biaxial (+) with α = 1.579(1), β = 1.586(1) and γ = 1.620(1) (measured in white light). The measured 2V is 50(2)° and the calculated 2V is 50°. Dispersion is r < v, medium. The optical orientation is Y ≈ b; Z ^ c = 36° in obtuse β (note pseudomonoclinic symmetry). The mineral is non-pleochroic. The empirical formula, determined from electron-microprobe analyses, is (Mg0.94Cu0.03Mn0.02Ca0.01)Σ 1.00As0.96O5H3.19. Magnesiokoritnigite is triclinic, P, with a = 7.8702(7), b = 15.8081(6), c = 6.6389(14) Å, α = 90.814(6), β = 96.193(6), γ = 90.094(7)°, V = 821.06(19) Å3 and Z = 8. The eight strongest X-ray powder diffraction lines are [dobs Å (I)(hkl)]: 7.96(100)(020), 4.80(54)(101), 3.791(85)(10,210,1,31), 3.242(56)(02,1,012), 3.157(92)(21,30,230), 3.021(61)(11,141,21,221), 2.798(41)(02,032) and 1.908(43)(multiple). The structure, refined to R1 = 5.74% for 2360 Fo > 4σF reflections, shows magnesiokoritnigite to be isostructural with koritnigite and cobaltkoritnigite.

Impact of arsenopyrite contamination on agricultural soils and crops

Aerially and fluvially distributed fine mineral particles produced by mining operations are an important source of toxic elements, such as arsenic, in surface environments. Limited data exists on the short-term stability of these particles in agricultural soils and the associated risk of producing contaminated crops. This study investigated whether arsenopyrite (FeAsS), the principal arsenic ore, undergoes oxidation–dissolution at a rate that is relevant to crop growth, and evaluated the availability of the alteration products to common crops. Temperate and sub-tropical soils were spiked (0.1%m/m) with ground arsenopyrite (<63μm) and incubated for intervals of up to one year prior to analyses for phosphate-exchangeable arsenic and soluble sulfate (alteration indicators). Triticum aestivum (spring wheat) was grown in the spiked temperate soil to evaluate plant arsenic uptake. Arsenopyrite platelets were exposed to field soil conditions (2years) and examined for secondary alteration phases. Arsenopyrite oxidation–dissolution was extensive and rapid (≤66% in 180days) in both soils. The As concentration in seeds of plants from spiked soils (21.2nmolg−1 As) was significantly higher than for plants grown in control soils (1.88nmolg−1 As). Secondary Fe–O–As phases formed agglomerates and rims at the soil-mineral interface under field conditions.This study demonstrates that the contamination of agricultural soils with fine arsenopyrite particles is a serious hazard in soils formed under contrasting geological and climatic settings. Uptake of As into edible tissue and hence the risk to human health was, under the present experimental conditions, moderated by three key processes: (1) Passivation layer formation on the weathering arsenopyrite surfaces effectively halted oxidation–dissolution after 180days exposure to the soil environment; (2) Secondary phase formation efficiently sequestered arsenic from soil solution, reducing its mobility and therefore phytoavailability. (3) Spring wheat appeared to actively limit the translocation of arsenic to the edible tissues (seeds).

Hydrogen isotope analyses of alteration phases in the nakhlite martian meteorites

Secondary alteration phases, such as carbonates, smectite clays and Fe-oxides, are found within the martian meteorites. If these meteorites were seen to fall, the assumption can be reasonably made that the secondary phases have a martian origin. However, for martian meteorite finds, this is not the case. Deuterium/hydrogen (D/H) ratio analysis can be used to distinguish between terrestrial and martian secondary alteration phases – the martian atmosphere is currently five times enriched in deuterium compared to terrestrial seawater, producing a deuterium enrichment in the martian alteration phases large enough to be detected with modern ion microprobe techniques. We aimed to measure the D/H ratio of the iddingsite-like alteration veins in the nakhlite martian meteorites Nakhla, MIL 03346, MIL 090030 and Y 000593, to help confirm the martian origin of this material, and determine the relative amounts of terrestrial contamination in each meteorite. As an observed fall Nakhla is nominally uncontaminated by terrestrial alteration, and shows elevated δD values in its alteration veins. However, even the highest of these values is much below that of the martian atmosphere, indicating that terrestrial contamination, probably combined with fractionation effects between the martian atmosphere and the alteration material, have reduced the δD values of these veins. The speed of hydrogen isotope exchange in the nakhlite iddingsite-like alteration veins is demonstrated by the purely terrestrial δD values in the veins of Nakhla 110, a thin-section exposed to the terrestrial atmosphere since its preparation in 1998. Mineralogical heterogeneity also affects the hydrogen isotope exchange rate in these veins – the wide variation in δD within the veins of Nakhla and Y 000593 appears to be due to the heterogeneous nature of the vein material, where some phases exchange hydrogen with the atmosphere at a faster rate than others.

Soil mineralogy at the Mars Exploration Rover landing sites: An assessment of the competing roles of physical sorting and chemical weathering

Soils in Gusev Crater and Meridiani Planum derive primarily from a surface dominated by basalt. The modal mineralogy of primary (igneous) and secondary (alteration) phases in the soils is estimated using Mössbauer, MiniTES, and APXS spectra. Primary minerals include plagioclase, pyroxene, and olivine with less common apatite, magnetite, and chromite. Secondary phases are dominated by sulfates, and include nanophase oxides, chlorides, hematite, and are assumed to include amorphous silica and phyllosilicates. Most soil chemical compositions overlap with basalts indicating that despite the presence of a secondary component in the soils, they have not been significantly chemically weathered. We modeled the significance of olivine dissolution by acid‐S by iteratively removing the molar FeOT + MgO component (olivine proxy) from the mean bulk compositions of the Gusev rock classes Adirondack, Algonquin, and Irvine until none remained. Regardless of modeling conditions, acid‐S alteration cannot account for many soils in Gusev Crater that are either depleted or enriched in molar FeOT + MgO, although it is a process capable of explaining some soil compositions. Based on a rock and mineral mixing model, supports our hypothesis for soil formation that consists of surface comminution by impact gardening, followed by compositional modification by hydrodynamic sorting and admixing of secondary components, including phyllosilicates and sulfates. Such a physical process can produce the range of molar FeOT + MgO in soils by concentrating or depleting specific minerals. For example, dust and fine sands are enriched in molar FeOT + MgO relative to coarse sand, which suggests accumulation of more mafic phases in finer grain fractions.

Radionuclide release from research reactor spent fuel

Numerous investigations with respect to LWR fuel under non oxidizing repository relevant conditions were performed. The results obtained indicate slow corrosion rates for the UO 2 fuel matrix. Special fuel-types (mostly dispersed fuels, high enriched in 235U, cladded with aluminium) are used in German research reactors, whereas in German nuclear power plants, UO 2-fuel (LWR fuel, enrichment in 235U up to 5%, zircaloy as cladding) is used. Irradiated research reactor fuels contribute less than 1% to the total waste volume. In Germany, the state is responsible for fuel operation and for fuel back-end options. The institute for energy research (IEF-6) at the Research Center Jülich performs investigation with irradiated research reactor spent fuels under repository relevant conditions. In the study, the corrosion of research reactor spent fuel has been investigated in MgCl 2-rich salt brine and the radionuclide release fractions have been determined. Leaching experiments in brine with two different research reactor fuel-types were performed in a hot cell facility in order to determine the corrosion behaviour and the radionuclide release fractions. The corrosion of two dispersed research reactor fuel-types (UAl x -Al and U 3Si 2-Al) was studied in 400 mL MgCl 2-rich salt brine in the presence of Fe 2+ under static and initially anoxic conditions. Within these experimental parameters, both fuel types corroded in the experimental time period of 3.5 years completely, and secondary alteration phases were formed. After complete corrosion of the used research reactor fuel samples, the inventories of Cs and Sr were quantitatively detected in solution. Solution concentrations of Am and Eu were lower than the solubility of Am(OH) 3(s) and Eu(OH) 3(s) solid phases respectively, and may be controlled by sorption processes. Pu concentrations may be controlled by Pu(IV) polymer species, but the presence of Pu(V) and Pu(IV) oxyhydroxides species due to radiolytic effects cannot completely be ruled out. Solution concentrations of U were within the range of the solubility limits of the solid phase U(OH) 4(am). The determined concentrations of U and Am in solution were about one order of magnitude higher for the U 3Si 2-Al fuel sample. Here, the formation of U/Si containing secondary phase components and their influence on radionuclide solubility cannot be ruled out. Results of this work show that the U 3Si 2-Al and UAl x -Al dispersed research reactor spent fuel samples dissolved completely within the test period of 3.5 years in MgCl 2-rich brine in the presence of Fe 2+. In view of final disposal this means that these fuel matrices represent no barrier. The radionuclides will be released instantaneously. Cs (the long-lived isotope 135Cs is of special concern with respect to final disposal) and Sr were classified as mobile radionuclide species. For U, Am, Pu and Eu, a reimmobilization was observed. Sorption is the process which is assumed to be responsible for the reimmobilization of the long-lived actinide Am and the lanthanide Eu. Solution concentrations of U and Pu seem to be controlled by their solubility controlling solid phases.

Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of trioctahedral Mg-clay minerals. Alternative models assuming other elements (Ni, Al, Fe) in addition to Mg in the second shell could not be fitted successfully. Aqueous concentration data were used to calculate the speciation of the leaching solutions. Saturation index (SI) calculations indicate undersaturation with respect to NiCO 3 and NiSO 4·7H 2O, but oversaturation with respect to β-Ni(OH) 2. The latter result is probably due to the omission of Ni borate and Ni silicate complexes in the speciation calculations, for which formation constants are not available. With the help of estimation techniques, we could infer that such complexes would dominate the Ni speciation and consequently reduce the SI below the saturation of β-Ni(OH) 2. The μ-XRF maps show that Cs is uniformly distributed in the MW glass, since no region with high Cs concentration could be detected. The Cs L III-edge μ-XAS spectra were all very similar independently of the degree of alteration, indicating similar coordination environments of Cs in the core regions of the glass as well as in the secondary clays. These spectra largely differ from that measured for pollucite (a potential secondary Cs-phase in altered glasses) implying that the coordination environments of Cs in the MW glass and in pollucite are fundamentally different. The present study shows that μ-XRF and μ-XAS are essential tools in determining the fate and the retention mechanisms of radionuclides released from nuclear waste during aqueous alteration. Our spectroscopic analyses allowed us to exclude formation of specific Ni and Cs secondary solids (e.g. nepouite, β-Ni(OH) 2, pollucite) during the aqueous alteration. Ni and Cs are instead distributed as trace elements in the alteration phases formed by major elements during the leaching process. Our results imply that solid solution and/or adsorption equilibria, rather than pure phase solubility equilibria, are the adequate chemical models to determine Ni and Cs aqueous concentrations in performance assessments for radioactive waste repositories.

Radiation damage and alteration of zircon from a 3.3 Ga porphyritic granite from the Jack Hills, Western Australia

Complexly zoned zircons (19 grains, ∼ 3.3 Ga) from a porphyritic granite in the Jack Hills, Western Australia, have been investigated using electron microprobe analysis (EMPA) and transmission electron microscopy (TEM) in order to examine the effects of radiation as a function of dose, as well as the nano-scale microstructure and composition of impurities and secondary alteration phases. In back-scattered electron (BSE) images, zones with bright contrast consist of an almost unaltered zircon with limited amounts of impurity elements. In contrast, the dark zones contain higher concentrations of trace elements: U, Th, Pb, Fe, Y, Ce, Ca and Al. The cumulative doses due to alpha-decay in the dark zones are calculated to be 0.21–1.0 × 10 17 (alpha-decay events/mg), equivalent to 1.0–4.7 dpa (displacements per atom). These doses are much higher than the dose required for radiation-induced amorphization, as determined by ion-beam irradiation of synthetic zircon, 0.3–1.0 dpa (0–600 °C). However, based on high-resolution TEM observations, none of the zircons are fully amorphous, to the result of annealing under ambient conditions. The concentrations of Ca and Al, which was considered to indicate alteration, increase dramatically at a cumulative dose of 1.6 × 10 16 (alpha-decay events/mg). This is the dose at which the first percolation point occurs, as amorphous domains overlap and form an interconnected network. In the altered zones, nanocrystallites of zircon are present with a random orientation, and the amorphous matrix contains the impurity elements. Although the Ce-concentration is extremely high, 1–2 wt.%, the Ce anomaly, Ce/Ce⁎, does not vary significantly as a function of dose or degree of alteration, indicating that the LREE patterns were overprinted by the fluids with a similar Ce-anomaly. The valence of Ce analyzed by EELS (electron energy loss spectroscopy) is tetravalent in the altered zone, suggesting that the altering fluids were oxidizing.

Trivalent actinide coprecipitation with powellite (CaMoO4): Secondary solid solution formation during HLW borosilicate-glass dissolution

SummaryPowellite (CaMoO4) is one of the various crystalline secondary alteration phases which form during the corrosion of high level waste (HLW) glasses. Due to their structural variability, powellite can accommodate considerable chemical substitutions including trivalent actinides. Batch adsorption and coprecipitation experiments in mixed flow reactors have been used to study quantitatively the uptake of Cm(III) and Eu(III) (as a nonradioactive chemical homologue for trivalent actinides) from aqueous solution under repository relevant conditions. A metal ion concentration-independentKdof 1200 ml/g has been determined for adsorption above pH 4 up to 3 μmol/L Eu(III). The partition coefficient for coprecipitation varies between 10 and 800 depending on the precipitation rate. Time-resolved laser fluorescence spectroscopy has been used to study the aqueous complexation of Cm(III)/Eu(III) and MoO42-as well as their incorporation into the powellite crystal lattice during coprecipitation. A red shift of the Cm(III) fluorescence emission of the transition indicates the formation of aqueous CmMoO4+(598 nm) and Cm(MoO4)22-(601 nm) complexes. The incorporation of Cm(III) is indicated by a significant red shift. The corresponding lifetime of 165 μs indicates quench effects. A similar behaviour has been observed for Eu(III). The life time of the5D0-7F2transition is 350 μs for an incorporated Eu(III) species, suggesting also intrinsic quench effects, due to the local crystal field or impurities.

Radiation-induced defects in dickites from the El Berrocal granitic system (Spain): relation with past occurrence of natural radioelements

This study deals with the radiation-induced defects in fracture filling clay-minerals from the EI Berrocal U-deposit (Spain), which is considered as a natural analogue of a high-level nuclear waste repository in granitic rock. Mineralogical anal yses shows the widespread occurrence of dickite as a secondary alteration phase, together with various amounts of associated smectite, illite, carbonates and primary minerals. Native radiation-induced defects accumulated in the dickite and smectite structure are identified by electron paramagnetic resonance spectroscopy (EPR). They are distinguished by their spectroscopic parameters and thermal stability, and can be reproduced by artificial irradiation. The dickite defects are similar to the well-characterized features in natural kaolinites, including defects stable at the scale of geological periods. Dickite can thus be used as a natural dosimeter to trace radioelement transfer in relevant geological systems. The concentration of stable defects in dickites is related to the present dose-rates, assuming dosimetry parameters from model kaolinites and several scenarii for dickite ages inferred from major tectonic events. This study demonstrates that the El Berrocal dickites correspond to different generations having recorded retention or migration events of radioelements within the whole system.

Thermal expansion of hydrated six-coordinate silicon in thaumasite, Ca3Si(OH)6(CO3)(SO4)�12H2O

Thaumasite, Ca3Si(OH)6(CO3)(SO4)12H2O, occurs as a low-temperature secondary alteration phase in mafic igneous and metamorphic rocks, and is recognized as a product and indicator of sulfate attack in Portland cement. It is also the only mineral known to contain silicon in six-coordination with hydroxyl (OH)− that is stable at ambient P–T conditions. Thermal expansion of the various components of this unusual structure has been determined from single-crystal X-ray structure refinements of natural thaumasite at 130 and 298 K. No phase transitions were observed over this temperature range. Cell parameters at room temperature are: a= 11.0538(6) A, c=10.4111(8) A and V=1101.67(10) A3, and were measured at intervals of about 50 K between 130 and 298 K, resulting in mean axial and volumetric coefficients of thermal expansion (×10−5K−1); α a =1.7(1), α c =2.1(2), and α V =5.6(2). Although the unit cell and VIIICaO8 polyhedra show significant positive thermal expansion over this temperature range, the silicate octahedron, sulfate tetrahedron, and carbonate group show zero or negative thermal expansion, with α V (VISiO6) = −0.6 ± 1.1, α V (IVSO4)=−5.8 ± 1.4, and α R (C–O)= 0.0 ± 1.8 (×10−5 K−1). Most of the thermal expansion is accommodated by lengthening of the R(O...O) hydrogen bond distances by on average 5σ, although the hydrogen bonds involving hydroxyl sites on VISi expand twice as much as those on molecular water, causing the [Ca3Si(OH)6(H2O)12]4+ columns to expand in diameter more than they move apart over this temperature range. The average Si–OH bond length of the six-coordinated Si atom 〈R(VISi–OH)〉 in thaumasite is 1.783(1) A, being about 0.02 A (˜20σ) shorter than VISi–OH in the dense hydrous magnesium silicate, phase D, MgSi2H2O6.

Samarium‐neodymium and rubidium‐strontium systematics of nakhlite Governador Valadares

Abstract— The Sm‐Nd systematics of whole‐rock and mineral separate samples from nakhlite Governador Valadares define a good 147Sm‐143Nd mineral isochron age of 1.37 ± 0.02 Ga. This age is in excellent agreement with the 39Ar‐40Ar and Rb‐Sr ages obtained previously for this meteorite. However, the Rb‐Sr isotopic data for our sample show that the isotopic system is disturbed. The lack of isotopic equilibrium is probably caused by the weathering of the sample as indicated by the presence of secondary alteration phases. The whole‐rock and acid‐washed mineral data yield a Rb‐Sr age of 1.20 ± 0.05 Ga, which probably represents a lower limit to the crystallization age of the rock. The petrographic evidence indicates that this meteorite is a clinopyroxene cumulate that probably crystallized in a subsurface sill (McSween, 1994). Thus, the Sm‐Nd isotopic age probably represents the age of such a magmatic event. The initial ε143Nd value determined for the rock at 1.37 Ga is +17 ± 1, indicating that the parent magma of the rock came from a light‐rare‐earth‐element‐depleted source of 147Sm/144Nd = ∼0.237 based on a simple two‐stage evolution model. Results of the same model calculation for the initial 87Sr/86Sr ratio of the rock suggest that its source material was depleted in 87Rb/86Sr by ∼50% relative to the estimated martian value at 1.37 Ga. Both the high Sm/Nd and low Rb/Sr values support a clinopyroxene‐rich cumulate source for the genesis of the nakhlite Governador Valadares. Furthermore, our Sm‐Nd age and ε143Nd data and the previously published ε142Nd datum for the rock (Harper et al., 1995) are consistent with early differentiation of the parent planet, formation of cumulate sources ∼4.56 Ga ago, and late melting of the sources and formation of the rock ∼1.37 Ga ago. The good agreement of isotopic ages and petrographic features among Governador Valadares, Nakhla, and Lafayette strongly suggests that all three nakhlites have undergone similar evolutionary histories. The nakhlite age data suggest that isotopic heterogeneity in the martian mantle sources existed up to ∼1.37 Ga ago and early mantle structures probably have not been disturbed for a significant portion of martian history.