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    Recommended nomenclature of epidote-group minerals
    (GeoScience World, 2006) Armbruster, Thomas; Bonazzi, Paola; Akasaka, Mashide; Bermanec, Vladimir; Chopin, Christian; Giere, Reto; Heuss-Aßbichler, Soraya; Liebscher, Axel; Menchetti, Silvio; Pan, Yuanming; Pasero, Marco
    Epidote-group minerals are monoclinic in symmetry and have topology consistent with space group P21/m and the general formula A2M3[T2O7][TO4](O,F)(OH,O). Zoisite is an orthorhombic polymorph of clinozoisite Ca2Al3[Si2O7][SiO4]O(OH) and is thus not considered a member of the epidote-group. Epidote-group minerals are divided into three subgroups. (1) Members of the clinozoisite subgroup are derived from the mineral clinozoisite Ca2Al3[Si2O7][SiO4]O(OH) by homovalent substitutions only. The key cation- and anion-sites are A1 = M2+, A2 = M2+, M1 = M3+, M2 = M3+, M3 = M3+, O4 = O2-, O10 = (OH)-. In other words, the dominant valence as listed above must be maintained. (2) Members of the allanite subgroup are REE-rich minerals typified by the eponymous mineral “allanite”. This subgroup may be derived from clinozoisite by homovalent substitutions and one coupled heterovalent substitution of the type A2(REE)3+ + M3M2+ → A2Ca2+ + M3M3+. Thus the valences on the key sites are: A1 = M2+, A2 = M3+, M1 = M3+, M2 = M3+, M3 = M2+, O4 = O2-, O10 = (OH)-. (3) Members of the dollaseite subgroup are REE-rich minerals typified by the eponymous mineral “dollaseite”. This subgroup may be derived from clinozoisite by homovalent substitutions and two coupled heterovalent substitutions of the type A2(REE)3+ + M3M2+ → A2Ca2+ + M3M3+ and M1M2+ + O4F-→ M1M3+ + O4O-2. Thus the valences on the key sites are: A1 = M2+, A2 = M3+, M1 = M2+, M2 = M3+, M3 = M2+, O4 = F-, O10 = (OH)-. The key cation-sites M3 and A1 (and, in principle, M2) determine the root name. In both clinozoisite and allanite subgroups no prefix is added to the root name if M1 = Al. The prefixes ferri, mangani, chromo, and vanado indicate dominant Fe3+, Mn3+, Cr3+, and V3+ on M1, respectively. In the dollaseite subgroup no prefix is added to the root name if M1 = Mg. Otherwise a proper prefix must be attached; the prefixes ferro and mangano indicate dominant Fe2+ and Mn2+ at M1, respectively. The dominant cation on A2 (other than Ca) is treated according to the Extended Levinson suffix designation. This simple nomenclature requires renaming of the following approved species: Niigataite (old) = clinozoisite-(Sr) (new), hancockite (old) = epidote-(Pb) (new), tweddillite (old) = manganipiemontite-(Sr) (new). Minor modifications are necessary for the following species: Strontiopiemontite (old) = piemontite-( Sr) (new), androsite-(La) (old) = manganiandrosite-(La) (new). Before a mineral name can be assigned, the proper subgroup has to be determined. The determination of a proper subgroup is made by the dominating valence at M3, M1, and A2 expressed as M2+ and or M3+, not by a single, dominant ion (i.e., Fe2+, or Mg, or Al). In addition, the dominant valence on O4: X- or X2- must be ascertained. [M2+]A2 > 0.50, [M3+]M3 > 0.50 → clinozoisite subgroup, [M3++ M4+]A2 > 0.50, [M2+]M3 > 0.50 → allanite subgroup, {[M2+]M3+M1 – [M3++ M4+]A2 } > 0.50 and [X-]O4 > 0.5 → dollaseite subgroup. Coupled heterovalent substitutions in epidote-group minerals require a special application of the so-called 50 % rule in solid-solution series. (1) Clinozoisite subgroup: The dominant trivalent cation on M3 determines the name, whereas the A2 cation appearing in the suffix has to be selected from among the divalent cations. (2) Allanite and dollaseite subgroups: For the sites involved in the charge compensation of a heterovalent substitution in A2 and O4 (i.e. M3 in the allanite subgroup; M3 and M1 in the dollaseite subgroup), identification of the relevant end-member formula must take into account the dominant divalent charge-compensating octahedral cation (M2+) and not the dominant cation in these sites. Formal guidelines and examples are provided in order to determine a mineral “working name” from electron-microprobe analytical data.
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    Widespread Archean basement beneath the Yangtze craton
    (GeoScience World, 2006) Zheng, Jianping; Griffin, William L; O’Reilly, Suzanne Y.; Zhang, Ming; Pearson, Norman; Pan, Yuanming
    The age distribution of the crust is a fundamental parameter in modeling continental evolution and the rate of crustal accretion through Earth’s history, but this is usually estimated from surface exposures. The exposed Yangtze craton in eastern China consists mainly of Proterozoic rocks with rare Archean outcrops. However, the U-Pb ages and Hf isotope systematics of xenocrystic zircons brought to the surface in lamproite diatremes from three Proterozoic outcrop areas of the craton suggest the widespread presence of unexposed Archean basement, with zircon age populations of 2900–2800 Ma and 2600– 2500 Ma and Hf model ages of 2.6 to ca. 3.5 Ga or older. The zircons also record thermal events reworked on the craton ca. 2020 Ma (remelting of older crust) and 1000–850 Ma (addition of juvenile mantle material). The observation of deep crust significantly older than the upper crust will require revision of models for the rates of crustal generation through time.
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    Equilibrium shapes of two and three dimensional two-phase rotating fluid drops with surface tension: effects of inner drop displacement
    (American Institute of Physics, 2022-11-01) Butler, Samuel
    The shapes of rotating fluid drops held together by surface tension is an important field of study in fluid mechanics. Recently, experiments with micron-scale droplets of liquid helium have been undertaken and it has proven useful to compare the shapes of the resultant superfluid droplets with classical analogs. If the helium is a mixture of He3 and He4, two phases are present. In a recent paper, the shapes of rotating two phase fluid droplets were calculated where the inner drop was constrained to stay at the drop center. The outer shapes and dimensionless rotation rate-angular momentum relationships were shown to be similar to single phase drops provided that the density and surface tension scales were chosen appropriately. In the current paper, I investigate models in which the inner drop can displace from the centre. In order to simplify the analyses, two dimensional drops are first investigated. I show that the inner drop is unstable in the centre position if its density is greater than the outer density and that the inner drop will move towards the outer boundary of the drop in these cases. When the inner drop has a higher density than the outer drop, the moment of inertia of displaced inner drops is increased relative to centered drops and hence the kinetic energy is decreased. Shapes of two and three dimensional drops, rotation rate-angular momentum and kinetic and surface energy relationships are investigated for off-axis inner drops with parameters relevant to recent liquid He experiments.
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    Trace element-mineral associations in modern and ancient iron terraces in acid drainage environments
    (Elsevier, 2016-07-31) Cruz-Hernandez, Pablo; Pérez-López, Rafael; Parviainen, Annika; Lindsay, Matthew B. J.; Nieto, José M.
    Iron-rich sediments commonly cover riverbeds that have been affected by acid drainage associated with sulfide-mineral oxidation. Freshly-formed precipitates correspond to poorly-crystalline oxyhydroxysulfates that recrystallize over time. This study examined the distribution and mineral association of trace elements (e.g., As, Cu, Zn) in modern and ancient (~ 6 Ma) Fe terraces in the Tinto river basin, Spain. The mineral composition of the terraces was determined by Raman μ-spectroscopy. Chemical digestions, electron probe microanalyses, and synchrotron-based μ-X-ray fluorescence mapping were used to examine As, Cu, and Zn distribution and corresponding mineral associations. Fresh precipitates at modern terrace surfaces were dominated by schwertmannite, which contained high As, Cu, Mn, and Zn concentrations. However, schwertmannite transforms into goethite over days to weeks in the deeper part of the current terraces and into hematite over centuries. Affinity for trace elements was generally highest for schwertmannite and lowest for hematite, which suggests that their retention by Fe terraces decreases during mineral transformation. Hence, schwertmannite acts as temporary sink for contaminants, which are again released over long time periods. These findings should be considered for management and treatment of possible water resources affected by acid mine drainage.
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    Influence of As(V) on precipitation and transformation of schwertmannite in acid mine drainage-impacted waters
    (Schweizerbart science publishers, 2018-12-07) Cruz-Hernandez, Pablo; Carrero, Sergio; Pérez-Lópeza, Rafael; Fernandez-Martinez, Alejandro; Lindsay, Matthew B. J.; Dejoie, Catherine; Nieto, José M.
    Iron-rich sediments commonly cover riverbeds affected by acid mine drainage (AMD). Initial precipitates are often dominated by schwertmannite, which has an exceptionally high capacity to sequester As and other toxic elements. This poorly crystalline Fe oxyhydroxysulfate rapidly recrystallizes to goethite; however, the influence of trace elements on ageing rates and products is poorly understood. This study examined the influence of As(V) concentrations on the kinetics of schwertmannite precipitation and transformation. Schwertmannite was synthesized in the presence of various initial dissolved As concentrations (i.e., 0–2 mM) and subsequently aged at 40, 60 or 85 °C for 1 h to 300 d. The initial As concentration had a profound impact on schwertmannite precipitation and transformation. Schwertmannite precipitation was inhibited at higher initial As concentrations in favor of pseudo-amorphous Fe-hydroxyarsenate formation. Schwertmannite transformation to goethite was accompanied by sulfate release and, over longer time, As release. Pair distribution function (PDF) analysis of high-energy X-ray diffraction (HEXD) patterns revealed that increasing initial As concentration produced structural defects in associated precipitates. Schwertmannite precipitation exerts an important control on As mobility in AMD-impacted waters; however, this study has demonstrated that the long-term stability of schwertmannite and associated precipitates should be considered when designing AMD remediation strategies and AMD treatment systems.
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    X-ray absorption spectroscopy and X-ray diffraction data for molybdenum minerals and compounds
    (Elsevier, 2022-09-13) Schoepfer, Valerie; Lindsay, Matthew B. J.
    We report Mo K- and LIII-edge X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) data collected for 15 molybdenum minerals and compounds sourced from museum collections, mineral dealers, and chemical suppliers. The samples were finely ground and analyzed at the Canadian Light Source synchrotron (Saskatoon, Canada). The L III-edge XAS data were collected in fluorescence and total electron yield mode, while the K-edge XAS data were collected in transmission and fluorescence modes. Molybdenum L III-edge spectra cover the X-ray absorption near edge structure (XANES) region and Mo K-edge spectra cover the extended X-ray absorption fine structure (EXAFS) region. Tabulated XAS data are provided to support analysis of XAS data obtained for geological or environmental research. Furthermore, Mo K-edge EXAFS and L III-edge XANES spectra, the k3 weighted oscillatory χ(k) functions, and the Fourier-transforms in χ(R) of these K-edge data are presented graphically. Corresponding XRD data were collected as two-dimensional images against an area detector and integrated to form line scans. The data were collected at a wavelength of 0.68866 Å (18 keV) and is tabulated and presented graphically over a 0-40 °2Q range. This dataset is intended to be used as reference material for a variety of rare and common Mo phases.
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    Repartitioning of co-precipitated Mo(VI) during Fe(II) and S(-II) driven ferrihydrite transformation
    (Elsevier, 2022-08-29) Schoepfer, Valerie; Lindsay, Matthew B. J.
    Molybdenum is an essential element for most biological systems. Biosynthesis of Mo-enzymes that support global biogeochemical cycles of N, C, and S depends upon bioavailable molybdate (MoO42−). Interactions with Fe(III) (oxyhydr)oxides can limit Mo bioavailability in aerobic environments, while redox-driven mineral transformations can enhance Mo sequestration. Here, we examine Mo repartitioning during Fe(II) and S(-II) driven ferrihydrite transformation under anaerobic conditions. We reacted Mo(VI) co-precipitated 2-line ferrihydrite with Fe(II)(aq) or S( II)(aq) and monitored geochemical and mineralogical changes over time. Inductively coupled plasma–mass spectrometry (ICP–MS) and synchrotron powder X-ray diffraction (XRD) results revealed rapid Fe(II)(aq) and S(-II)(aq) uptake and limited Mo release during extensive ferrihydrite transformation to goethite [α-FeOOH] and lepidocrocite [γ-FeOOH] in the Fe(II) and S( II) experiments. Transmission electron microscopy–selected area electron diffraction (TEM-SAED), coupled with Mo LIII-edge and K-edge X-ray absorption near edge structure (XANES) spectroscopy, revealed partial Mo(VI) reduction and precipitation of kamiokite [Fe2MoIV3O8] and sidwillite [MoVIO3‧2H2O] in both experiments. Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Mo K-edge revealed Mo-O, Mo-Fe and Mo-Mo bonding consistent with kamiokite precipitation in both Fe(II) and S(-II) experiments, and the absence of Mo-S bonding in the S(-II) experiments. Similar Mo(VI) repartitioning pathways during Fe(II) and S( II) driven ferrihydrite transformation suggests that: (i) Fe(II) served as the electron donor for ferrihydrite transformation in both experiments, with Fe(II)(aq) likely produced in situ via ferrihydrite sulfidation in the S( II) experiments; and (ii) co-precipitation inhibited Mo release and limited subsequent interactions S(-II)(aq) during ferrihydrite transformation. Overall, our findings indicate that initial association with FeOx phases can strongly influence Mo sequestration pathways in anaerobic environments.
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    Geochemical characteristics of oil sands fluid petroleum coke
    (Elsevier, 2016-11-30) Nesbitt, Jake A.; Lindsay, Matthew B. J.; chen, ning
    The geochemical characteristics of fluid petroleum coke from an oil sands mine in the Athabasca Oil Sands Region (AOSR) of northern Alberta, Canada were investigated. Continuous core samples were collected to 8 m below surface at several locations (n = 12) from three coke deposits at an active oil sands mine. Bulk elemental analyses revealed the coke composition was dominated by C (84.2 ± 2.3 wt. %) and S (6.99 ± 0.26 wt. %). Silicon (9210 ± 3000 mg kg−1), Al (5980 ± 1200 mg kg−1), Fe (4760 ± 1200 mg kg−1), and Ti (1380 ± 430 mg kg−1) were present in lesser amounts. Vanadium (1280 ± 120 mg kg−1) and Ni (230 ± 80 mg kg−1) occurred at the highest concentrations among potentially-hazardous minor and trace elements. Sequential extractions revealed potential for release of these elements under field-relevant conditions. Synchrotron powder X-ray diffraction revealed the presence of Si and Ti oxides, organically-complexed V and hydrated Ni sulfate, and provided information about the aromatic carbon matrix. X-ray absorption near edge structure (XANES) spectroscopy at the V and Ni K-edges revealed that these metals were largely hosted in porphyrins and similar organic complexes throughout coke grains. Slight variations among V and Ni K-edge spectra were largely attributed to slight variations in local coordination of V(IV) and Ni(II) within these organic compounds. However, linear combination fits were improved by including reference spectra for phases with octahedrally-coordinated V(III) and Ni(II). Sulfur and Fe K-edge XANES confirmed that thiophenic coordination and pyritic-ilmenitic coordination are predominant, respectively. These results provide new information on the geochemical and mineralogical composition of oil sands fluid petroleum coke and improve understanding of potential controls on associated water chemistry.
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    Aqueous- and solid-phase molybdenum geochemistry of oil sands fluid petroleum coke deposits, Alberta, Canada
    (Elsevier, 2018-11-12) Robertson, Jared M.; Nesbitt, Jake A.; Lindsay, Matthew B. J.
    Fluid petroleum coke generated at oil sands operations in the Athabasca Oil Sands Region of northern Alberta, Canada, contains elevated concentrations of molybdenum (Mo) and other metals including nickel (Ni) and vanadium (V). Solid-phase Mo concentrations in fluid petroleum coke are typically 10 to 100 times lower than V and Ni, yet dissolved Mo concentrations in associated pore waters are often comparable with these metals. We collected pore water and solids from fluid petroleum coke deposits in the AOSR to examine geochemical controls on Mo mobility. Dissolved Mo concentrations increased with depth below the water table, reaching maxima of 1.4 to 2.2 mg L-1, within a mixing zone between slightly acidic and oxic meteoric water and mildly alkaline and anoxic oil sands process-affected water (OSPW). Dissolved Mo concentrations decreased slightly with depth below the mixing zone. X-ray absorption spectroscopy revealed that Mo(VI) and Mo(IV) species were present in coke solids. The Mo(VI) occurred as tetrahedrally coordinated MoO42- adsorbed via inner- and outer-sphere complexation, and was coordinated in an environment similar to Fe-(hydr)oxide surface complexes. The OSPW likely promoted desorption of outer-sphere Mo(VI) complexes, resulting in higher dissolved Mo concentrations in the mixing zone. The principal Mo(IV) species was MoS2, which originated as a catalyst added upstream of the fluid coking process. Although MoS2 is likely stable under anoxic conditions below the mixing zone, oxidative weathering in the presence of meteoric water may promote long-term Mo release.
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    Mineralogy and geochemistry of oil sands froth treatment tailings: Implications for acid generation and metal(loid) release
    (Elsevier, 2019-02-04) Lindsay, Matthew B. J.; Vessey, Colton; Robertson, Jared M.
    Froth treatment tailings (FTT) are one of three principal tailings streams generated during bitumen extraction at oil sands mines in northern Alberta, Canada. Unlike the coarse tailings and fluid fine tailings, FTT are enriched in sulfide-minerals content and exhibit the potential for acid generation and metal(loid) leaching. However, the mineralogical and geochemical characteristics of this sulfide-bearing tailings stream remain poorly constrained. We examined samples of fresh FTT (n = 3) and partially-weathered FTT collected from a sub-aerial beach deposit (n = 15). X-ray diffraction revealed that weathering-resistant silicates, phyllosilicates, and oxides dominated (85 ± 7.3 wt. %) the FTT mineral assemblage, while sulfides (6.2 ± 3.6 wt. %) and carbonates (8.9 ± 4.3 wt. %) were relatively minor phases. Pyrite [FeS2] was the principal sulfide in all samples, while minor amounts of marcasite [FeS2] occurred only in beach samples. Sulfide mineral textures were highly variable and included euhedral to subhedral pyrite crystals, discrete and clustered pyrite framboids, and marcasite replacements of pyrite framboids. Siderite [FeCO3] accounted for 55 to 90 % of all carbonates, while dolomite [CaMg(CO3)2], calcite [CaCO3] and ankerite [Ca(Fe,Mg,Mn)(CO3)2] accounted for the remainder. Statistical analysis of bulk geochemical compositions suggested that environmentally-relevant metal(loid)s, including As, Cu, Co, Fe, Mn, Ni, Pb and Zn, were likely associated with sulfides, carbonates and, to a lesser extent, phyllosilicates. Electron probe microanalyses revealed a wide range of As, Cu, Co, Mn, Ni and Zn concentrations in pyrite, with As and Cu concentrations elevated in framboids. Rare earth elements (REEs), Th and U also occurred at elevated concentrations and statistical analyses suggest they are associated with zircon and, potentially, monazite and xenotime. Static acid-base accounting (ABA) tests indicated that all FTT samples are potentially acid generating. Our study describes the mineralogical and geochemical characteristics of oil sands FTT, and indicates that oxidative weathering has the potential to generate acidic drainage containing elevated dissolved concentrations of several metal(loid)s.
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    Aqueous vanadate removal by iron(II)-bearing phases under anoxic conditions
    (American Chemical Society (ACS) Publications, 2020-03-06) Vessey, Colton; Lindsay, Matthew B. J.
    Vanadium contamination is a growing environmental hazard worldwide. Aqueous vanadate (HxVVO4(3−x)− (aq)) concentrations are often controlled by surface complexation with metal (oxyhydr)oxides in oxic environments. However, the geochemical behaviour of this toxic redox sensitive oxyanion in anoxic environments is poorly constrained. Here we describe results of batch experiments to determine kinetics and mechanisms of aqueous H2VVO4− (100 μM) removal under anoxic conditions in suspensions (2.0 g L−1) of magnetite, siderite, pyrite, and mackinawite. We present results of parallel experiments using ferrihydrite (2.0 g L−1) and Fe2+(aq) (200 μM) for comparison. Siderite and mackinawite reached near complete removal (46 µmol g−1) of aqueous vanadate after 3 h and kinetic rates were generally consistent with ferrihydrite. Whereas magnetite removed 18 µmol g−1 of aqueous vanadate after 48 h and uptake by pyrite was limited. Uptake by Fe2+(aq) was observed after 8 h, concomitant with precipitation of secondary Fe phases. X ray absorption spectroscopy revealed V(V) reduction to V(IV) and formation of bidentate corner-sharing surface complexes on magnetite and siderite, and with Fe2+(aq) reaction products. These data also suggest that V(IV) is incorporated into the mackinawite structure. Overall, we demonstrate that Fe(II)-bearing phases can promote aqueous vanadate attenuation and, therefore, limit dissolved V concentrations in anoxic environments.
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    Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study
    (American Chemical Society (ACS) Publications, 2020-03-25) Vessey, Colton; Schmidt, Michael P.; Abdolahnezhad, Mojtaba; Peak, Derek; Lindsay, Matthew B. J.
    Vanadium (V) has been a useful trace metal in describing Earth’s biogeochemical cycling and development of industrial processes; however, V has recently been recognized as a potential contaminant of concern. Although Fe (oxyhydr)oxides are important sinks for aqueous V in soils and sediments, our understanding of adsorption mechanisms is currently limited to mononuclear species (i.e., HxVO4(3–x)–). Here we use in situ attenuated total reflectance – Fourier transform infrared spectroscopy to examine sorption mechanisms and capacity for (poly)vanadate attenuation by ferrihydrite and hematite from pH 3 to 6. Adsorption isotherms illustrate the low affinity of polyvanadate species for ferrihydrite surfaces compared to hematite. Mononuclear V species (i.e., [HxVO4](3−x)− and VO2+) were present at all experimental conditions. At low surface loadings and pH 5 and 6, H2VO4− adsorption onto ferrihydrite and hematite surfaces results from formation of inner sphere complexes. At [V]T above 250 µM, adsorbed polynuclear V species in this study include H2V2O72− and V4O124−. Whereas, HV10O286−, H3V10O285−, and NaHV10O284− are the predominant adsorbed species at pH 3 and 4 and elevated [V]T. Surface polymers were identified on hematite at all experimental pH values, whereas polymeric adsorption onto ferrihydrite was limited to pH 3 and 4. These results suggest that hematite offers a more suitable substrate for polymer complexation compared to ferrihydrite. Our results demonstrate the pH and concentration dependant removal of (poly)vanadate species by Fe(III) (oxyhydr)oxides, which has implications for understanding V mobility, behaviour, and fate in the environment.
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    Structural Incorporation of Sorbed Molybdate during Iron(II)-Induced Transformation of Ferrihydrite and Goethite under Advective Flow Conditions
    (American Chemical Society (ACS) Publications, 2020-06-08) Schoepfer, Valerie; Qin, Kaixuan; Robertson, Jared M.; Das, Soumya; Lindsay, Matthew B. J.
    Aqueous Fe(II) can induce recrystallization of ferrihydrite and goethite [α‑FeOOH] to their more crystalline or molecularly homogenous counterparts. Despite common association with these and other Fe(III) (oxyhydr)oxides, relationships between Fe(II)-induced transformation and Mo mobility remain poorly constrained. We conducted laboratory column experiments to examine repartitioning of sorbed Mo during Fe(II)-induced transformation of ferrihydrite and goethite under advective flow conditions. We first pumped (~0.25 L d−1) artificial groundwater containing 0.1 mM MoO42− and buffered to pH 6.5 through columns packed with ferrihydrite- and goethite-coated sand until > 90 % Mo breakthrough was observed. Extended X-ray absorption fine structure (EXAFS) spectroscopy shows that initial MoO42− attenuation resulted from inner sphere complexation of MoO4 tetrahedra at ferrihydrite and goethite surfaces. We then pumped Mo-free anoxic artificial groundwater containing 0.2 mM or 2.0 mM Fe(II) through the columns until effluent Mo concentrations remained < 0.005 mM. Raman spectroscopy shows that Fe(II) introduction induced transformation of both ferrihydrite and goethite to lepidocrocite. Additionally, Fe(II) introduction mobilized 4 to 34 % of sorbed Mo and total mass release was greater for (i) ferrihydrite compared to goethite columns and (ii) low Fe(II) compared to high Fe(II) influent. Effluent pH decreased to ~5.8 for columns receiving the high Fe(II) influent and returned to pH 6.5 after 5 to 10 pore volumes. EXAFS spectroscopy indicates that structural incorporation of MoO6 octahedra into neoformed phases contributes to Mo retention during Fe(II) induced transformation. Our results offer new insight into Mo repartitioning during Fe(II)-induced transformation of Fe(III) (oxyhydr)oxides and, more generally, controls on Mo mobility in geohydrologic systems.
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    Molybdenum(VI) sequestration mechanisms during iron(II)-induced ferrihydrite transformation
    (American Chemical Society (ACS) Publications, 2021-08-04) Schoepfer, Valerie; lum, jullieta; Lindsay, Matthew B. J.
    Adsorption and coprecipitation reactions with Fe(III) (oxyhydr)oxides contribute to Mo(VI) attenuation within geohydrologic systems. Redox transitions within these systems can promote transformation of metastable phases, including ferrihydrite, and repartitioning of associated Mo(VI). Recent studies show that Mo(VI) coordination shifts from tetrahedral to octahedral during Fe(II)-induced ferrihydrite transformation. However, effects of initial conditions including solution pH, the Mo(VI) uptake mechanism, and Mo(VI) loading on repartitioning are not known. We performed batch experiments using ferrihydrite suspensions prepared with adsorbed or coprecipitated Mo(VI) (0, 25, and 100 μmol g–1) at two initial pH values (pH0; 5.0 and 6.5). We catalyzed ferrihydrite transformation under anoxic conditions by adding Fe(II)(aq) (0.5 mM) and monitored pH, [Mo]T, and [Fe]T over time. After 168 h, we collected reacted solids for analysis by powder X-ray diffraction (XRD), transmission electron microscopy-selected area electron diffraction (TEM-SAED), and Mo K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. XRD data indicate that bulk ferrihydrite transformation was limited in all but the pH0 6.5 coprecipitated Mo(VI) experiments. The TEM-SAED results reveal that nanoscale lepidocrocite and goethite formed at ferrihydrite surfaces in all experiments, whereas nanoscale bamfordite [FeMo2O6(OH)3·H2O] crystallites were observed in pH0 6.5 experiments. EXAFS models reveal changes in Mo(VI) coordination and bonding consistent with bamfordite precipitation combined with structural incorporation into neoformed goethite and lepidocrocite. Our results improve the understanding of Mo(VI) retention pathways in geohydrologic systems.
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    Ebullition enhances chemical mass transport across the tailings-water interface of oil sands pit lakes
    (Elsevier, 2021-12-09) Francis, Daniel; Barbour, S. Lee; Lindsay, Matthew B. J.
    Base Mine Lake (BML) was the first commercial-scale demonstration oil sands pit lake established in northern Alberta, Canada. Recent studies indicate that ebullition enhances internal mass loading of dissolved constituents during settlement and dewatering of methanogenic fine fluid tailings (FFT) below the overlying water cap. Here, we describe results of integrated field measurements and numerical modelling to (i) determine potential for ebullition and enhanced mixing within BML, and (ii) assess impacts on chemical mass transport across the tailings-water interface. We observed sharp increases in [CH4(aq)] with depth from < 0.1 mg L−1 immediately above the interface to > 60 mg L−1 over the upper 1.5 to 3.0 m of FTT. Thermodynamic modelling revealed that maximum [CH4(aq)] values represent 60 to 80 % of theoretical saturation, and corresponding total dissolved gas pressures approach or exceed fluid pressures. These findings supported integration of enhanced mixing into one-dimensional (1-D) advective-dispersive transport models, which substantially improved upon previous simulations of conservative tracer (i.e., Cl−) profiles and chemical mass fluxes. The models revealed a positive relationship between CH4(aq) saturation and enhanced mixing, showing that ebullition enhance internal mass loading. This information has potential to inform ongoing assessments of pit lake performance and support improved closure and reclamation planning at oil sands mines.
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    Geochemical conditions influence vanadium, nickel, and molybdenum release from oil sands fluid petroleum coke
    (Elsevier, 2022-01-07) Abdolahnezhad, Mojtaba; Lindsay, Matthew B. J.
    Petroleum coke is a potential source of vanadium (V), nickel (Ni), and molybdenum (Mo) to water resources in Athabasca Oil Sands Region (AOSR) of northern Alberta, Canada. Large stockpiles of this bitumen upgrading byproduct will be incorporated into mine closure landscapes and understanding the processes and conditions controlling the release and transport of these transition metals is critical for effective reclamation. We performed a series of laboratory column experiments to quantify V, Ni, and Mo release from fluid petroleum coke receiving meteoric water (MW), oil sands process-affected water (OSPW), and acid rock drainage (ARD) influents. We found that influent water chemistry strongly influences metal release, with variations among metals largely attributed to pH-dependent aqueous speciation and surface reactions. Cumulative V, Ni, and Mo mass release was greatest for columns receiving the low-pH ARD influent. Additionally, cumulative V and Mo mass release were greater in columns receiving OSPW compared to MW influent, whereas cumulative Ni mass release was greater in columns receiving MW compared to OSPW influent. Nevertheless, only a small proportion of total V, Ni, and Mo was released during the experiments, with the majority occurring during the first 10 pore volumes (PVs). This study offers insight into geochemical controls on V, Ni, and Mo release from fluid petroleum coke that supports ongoing development of oil sands mine reclamation strategies for landscapes that contain petroleum coke.
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    Acidic microenvironments in waste rock characterized by neutral drainage: Bacteria-mineral interactions at sulfide surfaces
    (MDPI, 2014-03-21) Dockrey, John W.; Lindsay, Matthew; Mayer, K. Ulrich; Beckie, Roger D.; Norlund, Kelsey L. I.; Warren, Lesley; Southam, Gordon
    Microbial populations and microbe-mineral interactions were examined in waste rock characterized by neutral rock drainage (NRD). Samples of three primary sulfide-bearing waste rock types (i.e., marble-hornfels, intrusive, exoskarn) were collected from field-scale experiments at the Antamina Cu–Zn–Mo mine, Peru. Microbial communities within all samples were dominated by neutrophilic thiosulfate oxidizing bacteria. However, acidophilic iron and sulfur oxidizers were present within intrusive waste rock characterized by bulk circumneutral pH drainage. The extensive development of microbially colonized porous Fe(III) (oxy)hydroxide and Fe(III) (oxy)hydroxysulfate precipitates was observed at sulfide-mineral surfaces during examination by field emission-scanning electron microscopy-energy dispersive X-ray spectroscopy (FE-SEM-EDS). Linear combination fitting of bulk extended X-ray absorption fine structure (EXAFS) spectra for these precipitates indicated they were composed of schwertmannite [Fe8O8(OH)6–4.5(SO4)1–1.75], lepidocrocite [γ-FeO(OH)] and K-jarosite [KFe3(OH)6(SO4)2]. The presence of schwertmannite and K-jarosite is indicative of the development of localized acidic microenvironments at sulfide-mineral surfaces. Extensive bacterial colonization of this porous layer and pitting of underlying sulfide-mineral surfaces suggests that acidic microenvironments can play an important role in sulfide-mineral oxidation under bulk circumneutral pH conditions. These findings have important implications for water quality management in NRD settings.
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    Sodium transport and attenuation in soil cover materials for oil sands mine reclamation
    (Elsevier, 2018-11-03) Vessey, Colton; Lindsay, Matthew; Barbour, S. Lee
    Reclamation soil covers are used in oil sands mine closure to support vegetative growth over tailings. Geochemical processes within these covers may impact solute transport during upward migration of oil sands process-affected water (OSPW) from the underlying tailings. In this study, we examined the geochemical processes controlling Na transport and attenuation within the peat and clay-till cover soils at Sandhill Fen in northern Alberta, Canada. We analyzed soil core samples collected along transects of this 54-ha pilot-scale oil sands mine reclamation wetland. The geochemical (Na, Ca, Mg, K, Cl, SO4, HCO3) and isotopic (δ2H, δ18O) compositions of extracted pore water were analyzed statistically to identify OSPW and fresh surface water within the cover. Depth-dependent trends in pore water sodium concentrations were not apparent, suggesting that the soil cover had been fully flushed by a mixture of OSPW and fresh surface water used to flood the fen. Relative concentrations of Na, Ca and Mg were used to define the extent of cation exchange within the clay cover. Complementary laboratory column experiments showed that cation exchange removed up to 50% of dissolved Na as the first pore volume of simulated OSPW passed through the peat and till. However, Na attenuation by these materials declined rapidly and was limited after 4 (peat) to 7 (till) pore volumes of OSPW flushing. Reactive transport modeling confirmed that cation exchange was the dominant control on Na attenuation and corresponding Ca and Mg release within the till and peat columns. Mineral precipitation-dissolution reactions also influenced dissolved Ca and Mg concentrations and, therefore, indirectly impacted Na attenuation. Overall, this study helps constrain the geochemical processes controlling Na transport and attenuation in oil sands reclamation soil covers exposed to OSPW, and indicates that the attenuation of Na from OSPW by these covers is short-lived.
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    Variability in timing and transport of Pleistocene meltwater recharge to regional aquifers
    (American Geophysical Union (AGU), 2021-10-07) Mowat, Aidan; Francis, Daniel; McIntosh, Jennifer; Lindsay, Matthew; Ferguson, Grant
    The impacts of Pleistocene glaciation on groundwater flow systems in sedimentary basins are widely recognized, but the timing and distribution of subglacial recharge events remain poorly constrained. We investigate the spatial and temporal variability of recharge events from glaciations over the last 2 million years in the Williston Basin, Canada. Integration of fluid chemistry, stable isotope data, and transport modeling indicate that meltwater arrived at depths of ∼600–1000 m in the northcentral region of the Williston Basin at two separate time periods, 75–150 and 300 ka, which we attribute to permeability differences between stacked aquifer systems. Our findings indicate that meltwater recharge extended along the northern margin of the Williston Basin as well as previously identified recharge areas to the east. Given the distance of measurements from recharge areas, evidence of recharge from the early to mid-Pleistocene appears to be preserved in the Williston Basin.
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    Isotopic and chemical assessment of the dynamics of methane sources and microbial cycling during early development of an oil sands pit lake
    (MDPI, 2021-12-03) Slater, Greg; Goad, Corey A.; Lindsay, Matthew; Mumford, Kevin G.; Colenbrander Nelson, Tara E.; Brady, Allyson; Jessen, Gerdhard L.; Warren, Lesley
    Water-capped tailings technology (WCTT) is a key component of the reclamation strategies in the Athabasca oil sands region (AOSR) of northeastern Alberta, Canada. The release of microbial methane from tailings emplaced within oil sands pit lakes, and its subsequent microbial oxidation, could inhibit the development of persistent oxygen concentrations within the water column, which are critical to the success of this reclamation approach. Here, we describe the results of a four-year (2015–2018) chemical and isotopic (δ13C) investigation into the dynamics of microbial methane cycling within Base Mine Lake (BML), the first full-scale pit lake commissioned in the AOSR. Overall, the water-column methane concentrations decreased over the course of the study, though this was dynamic both seasonally and annually. Phospholipid fatty acid (PLFA) distributions and δ13C demonstrated that dissolved methane, primarily input via fluid fine tailings (FFT) porewater advection, was oxidized by the water column microbial community at all sampling times. Modeling and under-ice observations indicated that the dissolution of methane from bubbles during ebullition, or when trapped beneath ice, was also an important source of dissolved methane. The addition of alum to BML in the fall of 2016 impacted the microbial cycling in BML, leading to decreased methane oxidation rates, the short-term dominance of a phototrophic community, and longer-term shifts in the microbial community metabolism. Overall, our results highlight a need to understand the dynamic nature of these microbial communities and the impact of perturbations on the associated biogeochemical cycling within oil sands pit lakes.