Platinum group metals in common plants of northern forests: developments in analytical methods, and the application of biogeochemistry to exploration strategies

All platinum-group metals (PGM) in ashed plant tissues, from an area of platinum mineralization in Saskatchewan, have been measured by neutron activation analysis of a NiS fire assay bead. Concentrations of up to 1350 ppb (ng/g) Pd, 880 ppb Pt, 49 ppb Rh, 37 ppb Ru, 24 ppb Ir, and 15 ppb Os occur in ashed twigs of black spruce (Picea mariana), indicating that the ratios of PGM uptake are about the same as those occurring in the bedrock. Plants growing on drift-covered diabase, known to have about 100 ppb PGM, contain up to 77 ppb Pt in ash, demonstrating the potential value of biogeochemical methods in helping to delineate platiniferous zones. Twigs of black spruce, jack pine, and labrador tea appear to be the optimum sample media in this environment.A rapid multi-element neutron activation analysis by direct irradiation of tissue permits measurement of 0.05 ppb Ir in dry material, or 2 ppb Ir in ashed samples. In view of the normally very low concentrations of Ir in plants, any detectable Ir probably indicates enrichment of PGM in the substrate.Comparison of several wet-chemical analytical methods indicates that the optimum (cost-effective) technique for detecting 1–2 ppb Pt, Pd, or Rh in 2-g samples of ash is by Te co-precipitation (following fusion and dissolution), and analysis by ICP-MS with sample introduction by electrothermal vaporization. However, care must be taken to ensure complete dissolution of all PGMs in the ash.     

1988 COMPILATION OF ELEMENTAL CONCENTRATION DATA FOR USGS AGV-1, GSP-1 AND G-2

Concentration data on up to 90 individual constituents in USGS AGV-1, GSP-1, and G-2 have been collected from 1270 journal articles and technical reports. These data are summarized in consensus (mean) values with uncertainties expressed as +/- one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables. Recommended values are proposed based upon data criteria used by NIST (National Institute of Standards and Technology, formerly the National Bureau of Standards or NBS).     

Flood exposure and social vulnerability in the United States

Natural Hazards - Human exposure to floods continues to increase, driven by changes in hydrology and land use. Adverse impacts amplify for socially vulnerable populations, who disproportionately...     

Phase contrast synchrotron X-ray microtomography of Ediacaran (Doushantuo) metazoan microfossils: Phylogenetic diversity and evolutionary implications

Microfossils from the Ediacaran Weng’an Phosphate Member of the Doushantuo Formation (Guizhou Province, southern China) have received widespread attention. The Doushantuo, which overlies the glacial deposits of the Nantuo Formation, was deposited following the Marinoan glaciation, the last extensive glaciation of Snowball Earth. Radiometric age dating indicates that the Doushantuo is older than 580 my, and hence that these microfossils are older than the Ediacara Biota. However, the diversity represented by these fossils has yet to be fully documented. A recent technological approach that has increasingly been used to image fossils, propagation phase contrast synchrotron X-ray microtomography, has allowed non-destructive study of both exterior and interior features of a variety of Doushantuo microfossils from the gray facies of the Weng’an Phosphate Member, cropping out along the axis of the Mt. Beidou anticline. Studies of Doushantuo embryos demonstrate the existence of a large suite of modern embryonic features, including macromeres and micromeres, cell lineage, polar lobes, compacted epithelia, equal and unequal cleavage, blastulation and gastrulation, and chorionic protection. Because embryos such as those here studied provide only a limited amount of phylogenetic information, and because adult metazoans of the types that produced these embryos have yet to be discovered in Doushantuo-age rocks, these fossilized embryonic forms can at present be assigned only to the various superclades represented amongst living Metazoa. The diversity of the embryos here studied suggests that the metazoan fauna of the Doushantuo may well have included animals of poriferan, cnidarian, and both protostomial (representatives possibly of basal protostome lineages) and deuterostomial affinity. If this interpretation is correct, it would then follow that the last common ancestor of the bilaterian metazoan lineage, as well as the last common ancestor of sponges, cnidarians and bilaterians, pre-dated deposition of the Doushantuo strata.     

Silicate melt removal and sulfide liquid retention in ultramafic rocks of the Duke Island Complex,Southeastern Alaska

Magmatic Ni-Cu-PGE sulfide mineralization occurs within olivine clinopyroxenite, hornblende-bearing clinopyroxenite, and magnetite-hornblende-rich rocks in the Ural-Alaskan-Type Duke Island Complex in Southeast Alaska. The addition of large amounts of sulfur from country rocks occurred during fractional crystallization of the parental magma when clinopyroxene was becoming a liquidus mineral. Textural interfaces between sulfide and silicate minerals are strongly interlobate, and differ significantly from net-textures that are developed in many Ni-Cu-PGE deposits. Sulfide-free olivine clinopyroxenite is an adcumulate; residual liquid was efficiently expelled from the accumulating crystal pile. A significant interstitial liquid component is observable only in the form of interstitial sulfide in the S-rich rocks. Rounded sulfide inclusions and blebby to vermicular sulfide-silicate intergrowths indicate that silicate crystallization occurred under conditions of sulfide saturation. The presence of dense sulfide liquid inhibited the growth of silicate minerals and led to the development of interlobate grain boundaries. Strong, localized wetting of sulfide liquids on crystallizing silicates, and downward percolation of sulfide liquid through a crystallizing mush may have contributed to the evolution of these textures. Residual silicate liquid was removed from the system due to a combination of buoyant advection and compaction, but dense sulfide liquid remained.     

Engineering characterization of hydraulic properties in a pilot rock cavern for underground LNG storage

Feasibility of storing LNG in a lined rock cavern was evaluated using a pilot cryogenic rock cavern constructed in Daejeon, Korea. The pilot program included hydrogeological and engineering characterization of the rock mass around the cavern, design and construction of a drainage system, and pilot operation of the cryogenic cavern. An appropriate drainage system is most important to protect the containment system of LNG from thermal shocks due to ice lenses and hydrostatic pressure of groundwater. As a part of the pilot program, this study focused on the evaluation of hydraulic and engineering properties of the rock mass around the cavern. For this purpose, engineering logging of the rock cores, single and cross-hole hydraulic tests, and recharge/drainage tests were performed using seven drilled holes with different trends and plunges. Three main joint sets were found from the logging of the rock cores, acoustic borehole televiewer, and window mapping. The orientations of the three major joint sets were 60/209, 40/171, and 29/331, which can provide the main groundwater flow paths. Mean RQD values ranged from 56 to 88, which were classified as fair and good, although varying with depth along single boreholes. Hydraulic conductivity from the single and cross-hole hydraulic tests estimated in the order of 10⁻⁶ or 10⁻⁷ m/s and corresponding transmissivity ranged between 10⁻⁵ and 10⁻⁶ m²/s. Permeable intervals identified from the hydraulic tests were mostly located above the cavern roof. Below the roof, the permeable zone was difficult to observe. According to the hydraulic communication tests performed for some designated intervals, hydraulic connection between boreholes was highly varied with depth or location, which indicated a very different distribution of water conducting joint sets along the boreholes. When water was injected at R1 with constant or varying flow rates, monotonous and stable seepage was observed at observation boreholes. From this, some stable drainage was expected even in relatively heavy rainfalls. When designing the drainage system of the cavern, the drainage holes should be orientated to maximize frequency of encountering the major joint sets and the permeable intervals identified from this study.     

Growth-strata geometry in fault-propagation folds: a case study from the Gafsa basin, southern Tunisian Atlas

The structural and sedimentological study of fault-propagation folds in Southern Tunisia highlights a special geometry of the growth strata (strata deposited simultaneously with the formation or growth of a fold). This distinct geometry is visible in the uppermost growth-strata beds and consists of one flank with unconformity as opposed to the other flank with perfect conformity. This geometry can be explained by the mechanism of fault-propagation folding, with asymmetrical flank dips and hinge migration kinematics. This kinematics was originally predicted by the fault-propagation fold model, which facilitates the study of this special geometry in a narrow domain of sedimentation-to-shortening ratios. A plot projection provides a generalisation of the results of all types of fault-propagation folds by revealing the expected geometry of the growth strata. This study constitutes one of the most complete examples of kinematic model validation on a field scale.     

Experimental determination of synthetic NdPO4 monazite end-member solubility in water from 21°C to 300°C: implications for rare earth element mobility in crustal fluids

The solubility of synthetic NdPO₄ monazite end-member has been determined experimentally from 21 to 300°C in aqueous solutions at pH = 2, and at 21°C and pH = 2 for GdPO₄. Measurements were performed in batch reactors, with regular solution sampling for pH measurement, rare earths and phosphorous analysis by inductively coupled plasma mass spectrometry (ICP-MS) coupled with a desolvation system. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to check that no reprecipitation of secondary phases occurred and that the mineral surfaces remained those of a monazite. Coupled with speciation calculations, measured solution compositions permitted the determination of NdPO₄ and GdPO₄ solubility products which are in general agreement with previous experimental determination on rhabdophane at 25°C, but showing that monazite is more than two orders of magnitude less soluble than inferred on the basis of previous thermodynamic estimates. The temperature evolution from 21 to 300°C of the equilibrium constant (K) of the NdPO₄ monazite end-member dissolution reaction given by:

     

Preliminary estimates of regolith generation and mobility in the Susquehanna Shale Hills Critical Zone Observatory,Pennsylvania, using meteoric 10Be

This study seeks to quantify the rate and timing of regolith generation in the Critical Zone at the Susquehanna Shale Hills Critical Zone Observatory (SSHO). Meteoric ¹⁰Be depth profiles were determined using measurements from 30 hillslope soil and bedrock core samples in an effort to constrain ¹⁰Be inventories. The SSHO is located in the temperate climate zone of central Pennsylvania and comprises a first-order watershed developed entirely on a Fe-rich, organic-poor, Silurian-aged shale. Two major perturbations to the landscape have occurred at SSHO in the geologically recent past, including significant and sustained periglacial activity until after the retreat of the Laurentide ice sheet (～21 ka) and deforestation during early colonial land-use. Bulk soil samples (n = 16) were collected at three locations along a planar hillslope on the southern ridge of the catchment, representing the ridge top, mid-slope and valley floor. Rock chip samples (n = 14) were also collected from a 24 m deep core drilled into the northern ridge top. All meteoric ¹⁰Be concentration profiles show a declining trend with depth, with most of the ¹⁰Be retained in the uppermost decimeters of the soil. Meteoric ¹⁰Be inventories are higher at the mid-slope and valley floor sample sites, at 3.71 ± 0.02 × 10¹⁰ at/cm² and 3.69 ± 0.02 × 10¹⁰ at/cm², than at the ridge top site (1.90 ± 0.01 × 10¹⁰ at/cm²). The ¹⁰Be inventory at the convex ridge top site implies a minimum residence time of ～10.6 ka, or if erosion is steady, an erosion rate of 19.4 ± 0.2 m/My.     

Experimental studies of equilibrium iron isotope fractionation in ferric aquo-chloro complexes

Here we compare new experimental studies with theoretical predictions of equilibrium iron isotopic fractionation among aqueous ferric chloride complexes (Fe(H₂O)₆³⁺, FeCl(H₂O)₅²⁺, FeCl₂(H₂O)₄⁺, FeCl₃ (H₂O)₃, and FeCl₄^-), using the Fe-Cl-H₂O system as a simple, easily-modeled example of the larger variety of iron-ligand compounds, such as chlorides, sulfides, simple organic acids, and siderophores. Isotopic fractionation (⁵⁶Fe/⁵⁴Fe) among naturally occuring iron-bearing species at Earth surface temperatures (up to ∼3‰) is usually attributed to redox effects in the environment. However, theoretical modeling of reduced isotopic partition functions among iron-bearing species in solution also predicts fractionations of similar magnitude due to non-redox changes in speciation (i.e., ligand bond strength and coordination number). In the present study, fractionations are measured in a series of low pH ([H⁺] = 5 M) solutions of ferric chloride (total Fe = 0.0749 mol/L) at chlorinities ranging from 0.5 to 5.0 mol/L. Advantage is taken of the unique solubility of FeCl₄^- in immiscible diethyl ether to create a separate spectator phase, used to monitor changing fractionation in the aqueous solution. Δ⁵⁶Fe_aq-eth = δ⁵⁶Fe (total Fe remaining in aqueous phase)−δ⁵⁶Fe (FeCl₄^- in ether phase) is determined for each solution via MC-ICPMS analysis.Both experiments and theoretical calculations of Δ⁵⁶Fe_aq-eth show a downward trend with increasing chlorinity: Δ⁵⁶Fe_aq-eth is greatest at low chlorinity, where FeCl₂(H₂O)₄⁺ is the dominant species, and smallest at high chlorinity where FeCl₃(H₂O)₃ is dominant. The experimental Δ⁵⁶Fe_aq-eth ranges from 0.8‰ at [Cl^-] = 0.5 M to 0.0‰ at [Cl^-] = 5.0 M, a decrease in aqueous-ether fractionation of 0.8‰. This is very close to the theoretically predicted decreases in Δ⁵⁶Fe_aq-eth, which range from 1.0 to 0.7‰, depending on the ab initio model.The rate of isotopic exchange and attainment of equilibrium are shown using spiked reversal experiments in conjunction with the two-phase aqueous-ether system. Equilibrium under the experimental conditions is established within 30 min.The general agreement between theoretical predictions and experimental results points to substantial equilibrium isotopic fractionation among aqueous ferric chloride complexes and a decrease in ⁵⁶Fe/⁵⁴Fe as the Cl^-/Fe³⁺ ion ratio increases. The effects on isotopic fractionation shown by the modeling of this simple iron-ligand system imply that ligands present in an aqueous environment are potentially important drivers of fractionation, are indicative of possible fractionation effects due to other speciation effects (such as iron-sulfide systems or iron bonding with organic ligands), and must be considered when interpreting iron isotope fractionation in the geological record.