Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

Adsorption mechanisms of trivalent gold on iron- and aluminum-(oxy)hydroxides. Part 1: X-ray absorption and Raman scattering spectroscopic studies of Au(III) adsorbed on ferrihydrite, goethite, and boehmite

Gold adsorption products on powdered ferrihydrite, goethite, and boehmite samples, prepared by reacting Au(III)-Cl solutions ([Au] = 4.2 × 10⁻⁵-9.0 × 10⁻³ M; [Cl] = 0.017-0.6 M) with these adsorbents at pH values of 4 to 9 and Au adsorption densities ranging from 0.046 to 1.53 μmol/m² were characterized using Au-L_III XAFS spectroscopy. The solutions (before and after uptake) were investigated by Raman scattering to determine speciation and by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) to determine solution composition. We present an analysis of several effects that are observed in the Au L_III-edge XAFS spectra, including X-ray beam-induced photo-reduction, multi-electronic excitations, disorder effects, and multiple scattering, that would complicate interpretation of the spectra if not accounted for. A combination of methods (spectral deconvolution, principal component analysis, spectral inversion, and wavelet analysis) was used to identify and quantify these effects, to characterize the nature of mixed ligands around gold, and to distinguish between multiple-scattering features and features due to next-nearest neighbors in the XAFS spectra.Analysis of the Au-L_III XAFS spectra showed that Au(III) is present as square-planar Au(III)(O,Cl)₄ complexes in the aqueous solutions and on the surfaces of the Al/Fe-(oxy)hydroxide adsorption samples with dominantly O ligands at pH > 6 and mixed O/Cl ligands at lower pH values. The EXAFS-derived Au-O and Au-Cl distances are 2.00(2) and 2.28(2) Å, respectively, and the magnitudes of the Debye-Waller factors and third cumulants from anharmonic analyses indicate very little thermal or positional disorder around Au(III) in the adsorption samples. Iron second neighbors are present around Au in the Au(III)/ferrihydrite and Au(III)/goethite adsorption samples, with Au-Fe distances of 3.1(1) and 3.3(1) Å. In boehmite, two sets of Au-Al distances were detected at 3.0(1) and 3.2(1) Å. A reverse Monte Carlo study of the XAFS spectroscopic data suggests the presence of a continuum of edge-shared AuO₄-FeO₆ distances, which cannot be described correctly by a classical model of these data in which only a mean distance (although severely under-estimated) is derived.     

An evaluation of glass prisms in boat docks to reduce shading of submerged aquatic vegetation in the lower St. Johns River,Florida

The effectiveness of glass prisms in boat docks was assessed to determine if shading impacts to submerged aquatic vegetation (SAV), primarilyVallisneria americana, were reduced. Six experimental docks, three with prisms and three without prisms, were constructed in the lower St. Johns River, Florida. SAV percent cover and photosynthetically active radiation (PAR) were monitored under each dock and in an adjacent control area with no experimental docks. Subsurface PAR during the growing season of the first year of the study was not significantly greater beneath docks having prisms than beneath docks without prisms. Postconstruction SAV monitoring (February 2000 to May 2002) revealed no significant differences in SAV percent cover between dock treatments, although coverage declined in both dock treatments and the control area. Declining water quality conditions at the study site clearly impacted the health of the SAV habitat as indicated by the decline in SAV coverage in the control area initially in the study. Given the subsequent resurgence of SAV in the control area, the additional light transmitted through the prisms did not appear to be biologically significant or adequate to counteract effects from larger-scale environmental stressors.     

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni–NiO or Co–CoO) and H₂O, with an inner gold–palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010). H₂O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9–10):985–994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333–1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni–NiO and Co–CoO buffers, which is incorrect since the melts are all undersaturated in H₂O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log $a_{{{\text{H}}_{ 2} {\text{O}}}}$ .     

Subcalcic diopsides from kimberlites: Chemistry,exsolution microstructures,and thermal history

Twenty-six subcalcic diopside megacrysts (Ca/(Ca+ Mg)) = 0.280–0.349, containing approximately 10 mol% jadeite, from 15 kimberlite bodies in South Africa, Botswana, Tanzania, and Lesotho, have been characterized by electron microprobe analysis, X-ray-precession photography, and transmission electron microscopy. Significant exsolution of pigeonite was observed only in those samples for which Ca/(Ca+Mg)0.320. The exsolution microstructure consists of coherent (001) lamellae with wavelengths ranging from 20 to 31 nm and compositional differences between the hosts and lamellae ranging from 10 to 30 mol% wollastonite. These observations suggest that the exsolution reaction mechanism was spinodal decomposition and that the megacrysts have been quenched at various stages of completion of the decomposition process.Annealing experiments in evacuated SiO₂ glass tubes at 1,150° C for 128 hours failed to homogenize microstructure, whereas, at 5 kbar and 1,150° C for only 7.25 hours, the two lattices were homogenized. This pressure effect suggests that spinodal decomposition in the kimberlitic subcalcic diopside megacrysts can only occur at depths less than 15 km; the cause of the effect may be the jadeite component in the pyroxene. Apparent quench temperatures for the exsolution process in the megacrysts range from 1,250° C to 990° C, suggesting that decomposition must have commenced at temperatures of more than 1,000° C.These P–T limits lead to the conclusion that, in those kimberlites where spinodal decomposition has occurred in subcalcic diopside megacrysts, such decomposition occurred at shallow levels (<15 km) and, at the present erosion level, temperatures must have been greater than 1,000° C.     

Structure of mineral glasses—I. The feldspar glasses NaAlSi3O8, KAlSi3O8, CaAl2Si2O8

The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO₂ glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO₂ glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results.     

Identification of microdetritus derived fromSpartina and its occurrence in the water column and intertidal sediments of Cumberland Basin,Bay of Fundy

A cellulose-specific staining procedure employing Herzberg’s chlor-zinc-iodide solution was developed to aid in the identification of microdetritus derived fromSpartina alterniflora and tested on samples of suspended and sedimented particulate matter collected in the Cumberland Basin at the head of the Bay of Fundy. Not all of the particles reacting positively to the stain could have been identified as originating fromSpartina on the basis of morphology alone, and the stain improved speed and confidence in identification even when particles could be identified morphologically.Spartina dominated particles greater than 100 μm while most of the smaller particles were amorphous aggregates of uncertain origin. In April 1985, at the start of the salt-marsh growing season, the average concentration of suspended microdetritus derived fromSpartina in Cumberland Basin surface water was 129 mg C m^?3 or 0.3–2.7% of the particulate organic carbon. The average concentration in intertidal sediments was 0.036 mg C g^?1 or 0.2–0.9% of the sediment organic carbon. Summing all reservoirs in the sediment (to a depth of 1 cm) and water column, the total amount of detritus originating fromSpartina in Cumberland Basin is 10–24% of the estimated annual net primary production of low marshS. alterniflora.     

Analysis of wax hydrocarbons in petroleum source rocks from the Damintun depression, eastern China, using high temperature gas chromatography

A detailed organic geochemical study; utilising petrography, biomarker hydrocarbon analysis and high temperature GC analysis of extractable wax hydrocarbon constituents was performed on four marginally oil window-mature source rocks from the Shahejie Formation (Eocene), Damintun depression in eastern China. The main maceral components in the source rocks were vitrinite, liptinite and exinite, with vitrinite being more abundant (>50 vol.%) in organic-lean samples whose TOC contents were between 1 and 2 wt.%. Large differences in pristane/phytane ratios suggested that the organic-rich samples were deposited in a less oxic depositional environment than that for the organic-lean rocks. The distribution of extractable wax hydrocarbons, determined by high temperature GC, showed a marked difference between these two sample types. The organic-rich samples contained high molecular weight hydrocarbons (HMWHCs) dominated by macrocrystalline n-alkanes (n-C₂₃–n-C₃₇, typically maximising at n-C₂₉), while the organic-lean samples contained lower amounts of extractable wax hydrocarbons but were relatively rich in microcrystalline components (> n-C₃₅). In all source rocks (Es3 and Es4), a noticeable odd-over-even predominance (OEP) of n-alkane chain lengths (up to n-C₆₅) was evident, consistent with a direct biological origin for the long n-alkyl chains. They were most probably formed during diagenesis from decarboxylation of predominantly even-carbon-numbered aliphatic acids originating from higher plant or lacustrine algal sources and/or were directly biosynthesised in hydrocarbon form. At least two other homologous series of branched/cyclic HMWHCs were observed, one of which was confirmed as a series of branched alkanes (probably methyl-branched). The carbon number distribution patterns of HMWHCs may be primarily controlled by thermal maturity and biogenic source input as well as being influenced by diagenetic reactions governed by depositional environmental conditions, as shown previously [Carlson, R.M.K., Teerman, S.C., Moldowan, J.M., Jacobson, S.R., Chan, E.I., Dorrough, K.S., Seetoo, W.C., Mertani, B., 1993. High temperature gas chromatography of high wax oils. In: Indonesian Petroleum Association, 22nd Annual Convention Proceedings. Jakarta, Indonesian, pp. 483–507. Carlson, R.M.K., Jacobsen, S.R., Moldowan, J.M., Chan E.I., 1994. Potential application of high temperature gas chromatography to Middle Eastern petroleum exploration and production. In: Al-Husseini, M.I. (Ed.), Geo'94, Vol 1., Selected Middle East Papers from The Middle East Petroleum Geoscience Conference, 1994; Gulf PetroLink. Manama, Bahrain, pp. 258–267]. Our study indicates for the first time that Es3 source rocks as well as Es4 facies contain HMWHCs. The distributions of extractable wax hydrocarbons suggest that both Es4 and Es3 members may potentially serve as important parent source rocks for generating waxy petroleum in this region.     

Early Mesoproterozoic evolution of midcontinental Laurentia: Defining the geon 14 Baraboo orogeny

New geochronologic data from midcontinental Laurentia demonstrate that emplacement of the 1476-1470 Ma Wolf River granitic batholith was not an isolated igneous event,but was accompanied by regional metamorphism,deformation,and sedimentation.Evidence for such metamorphism and deformation is best seen in siliciclastic sedimentary rocks of the Baraboo Interval,which were deposited closely following the1.65-1.63 Ga Mazatzal orogeny.In Baraboo Interval strata,muscovite parallel to slatey cleavage,in hydrothermal veins,in quartzite breccia,and in metamorphosed paleosol yielded ~(40)Ar/~(39)Ar plateau age s of 1493-1465 Ma.In addition,U-Th-total Pb dating of neoblastic overgrowths on detrital monazite gave an age of 1488±20 Ma,and recrystallized hematite in folded metapelite gave a mean U/Th-He age of 1411± 39 Ma.Post-Baraboo,arkosic polymictic conglomerate,which contains detrital zircon with a minimum peak age of 1493 Ma,was intruded by a 1470 Ma granite porphyry at the northeastern margin of the Wolf River batholith.This episode of magmatism,regional deformation and metamorphism,and sedimentation,which is designated herein as the Baraboo orogeny,provides a midcontinental link between the Picuris orogeny to the southwe st and the Pinware orogeny to the northeast,completing the extent of early Mesoproterozoic(Calymmian) orogenesis for 5000 km along the southern margin of Laurentia.This transcontinental orogen is unique among Precambrian orogenies for its great width(～1600 km),the predominance of ferroan granites derived from partial melting of lower continental crust,and the prevalence of re gional high T-P metamorphism related to advective heating by granitic magmas emplaced in the middle to upper crust.     

Natural fractionation of U/U

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the ²³⁸U/²³⁵U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed ²³⁶U-²³³U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ²³⁸U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ²³⁸U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ²³⁸U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ²³⁸U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ²³⁸U (−0.41‰ to −0.16‰) compared to seawater, which has δ²³⁸U of −0.41 ± 0.03‰. Granites define a range of δ²³⁸U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ²³⁸U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble U^VI to insoluble U^IV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that ²³⁸U/²³⁵U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in ²⁰⁷Pb/²⁰⁶Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.