Arsenic and lead mobility: From tailing materials to the aqueous compartment

This study concerns the mineralogy of the tailings of a former Ag–Pb mine (Auzelles district, France) and the contribution of the waste materials to the heavy metal dissemination in the environment. Accumulation of metals in fish flesh was reported and this pollution is attributed to past mining activities. Tailings were studied to establish the major transfer schemes of As and Pb in order to understand their mobility that leads to contamination of a whole ecosystem. Mineralogical investigation, solubility and compliance tests were performed to assess the stability of the metal-bearing phases. Among the various metallic elements measured, As and Pb show the highest bulk concentrations (up to 0.7% and 6.3% respectively) especially for samples presenting near neutral pH values. According to X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Electron Probe Micro-Analysis (EPMA) and micro-Raman spectrometry (μRS), tailings mineralogy still contain primary minerals such as sulfides (e.g., galena, pyrite), phosphates (monazite, apatite) and/or carbonates (e.g., (hydro-)cerussite, dolomite, siderite). Sulfates (e.g., anglesite, lanarkite, plumbojarosite and beudantite) are the main secondary metal-bearing phases with other interesting phases accounting for metals mobility such as Fe and/or Pb and/or Mn oxides (e.g., lepidocrocite, goethite -up to 15 wt% of Pb was measured-, plumboferrite-type phase, mimetite). The lowest Pb solubilities were obtained at pH 8–9 and at a larger range than for As for which the lowest solubilities are reached around pH 6–7. At this minimum solubility pH value, Pb concentrations released still over exceed the National Environmental Quality Standards (NEQS), whatever the samples. The highest solubility is reached at pH 2 for both elements whatever the considered sample. This represents up to 51% of total Pb and up to 46% of total As remobilized and concentrations exceeding the NEQS. As and Pb released mainly depends on the Fe/Mn oxides (e.g., goethite, lepidocrocite) and carbonates (cerussite) which are the less stable phases. Compliance tests also show that Pb concentrations released are higher than the upper limit for hazardous waste landfills. Determination of the mineralogy allows understanding both the solubility and leaching test experiments results, as well as to forecast the impact of the residues on the water quality at a mid-term scale.     

Enstatite chondrites: Trace element clues to their origin

We have analyzed by RNAA 3 EH and 3 EL chondrites for 20 trace elements. Interelement correlations were examined visually and by factor analysis, to assess the effects of nebular fractionation and metamorphism.Refractory siderophiles (Ir, Os, Re) correlate with “normal siderophiles” (Ni, Pd, Au, Sb, and Ge) in EL's but not EH's; presumably these two element groups originally condensed on separate phases (CAI and metal), but then concentrated in metal during metamorphism. Sb and Ge are more depleted than the other three elements of the “normal” group, presumably by volatilization during chondrule formation.Volatiles are consistently more depleted in EL's than EH's, by factors >10× for the more volatile elements. Some of the stronger correlations are found for In-Tl, Tl-Bi, and Zn-Cd-In. These correlations are about equally consistent with predicted condensation curves for the solar nebula (especially for host phases with negative heats of solution, or for P = 0.1?1 atm) and with volatilization curves for artificially heated Abee, as determined by M E. Lipschutz and coworkers at Purdue. No decisive test between these alternatives is available at present, but the close correlation of Zn, Cd, In may eventually provide a crucial test.Factor analysis shows that 3 factors account for 93% of the variance; they seem to reflect volatile (F1), siderophile (F2), and chalcophile (F3) behavior. The element groupings agree largely with those recognized visually; they are listed with the inferred host phases. F1 (minor sulfide, probably ZnS): Zn, Cd, In, Br; F2 (CAI, later metal): Ir, Os. Re; F1, F2 (metal): Ni, Pd, Au, Ge, Sb; F3, F1 (FeS): Se, Te, Bi, Tl. These correlations differ to some extent from those obtained by Shaw (1974) in an earlier factor analysis, presumably because the new data are more homogeneous and extensive, especially for siderophiles. The new correlations also show that the cosmochemical behavior of some volatiles in E-chondrites differs from that predicted for ordinary chondrites, so that condensation curves for the latter are not strictly applicable.     

The equilibrium speciation of dissolved components in freshwater and sea water at 25°C and 1 atm pressure

A data base summarising the stability constants of more than 500 complexes is used to calculate speciation pictures for 58 trace elements in model seawater (pH 8.2) and freshwaters (pH 6 and 9). Consideration of the results provides a general summary of the chemical periodicity of the speciation of trace components in natural waters. The polarising power of an element ((cation charge)²/(radius), z²/r) provides a useful index to the degree of hydrolysis in aqueous solution. The fully hydrolysed elements with a high polarising power form distinct groupings in the periodic table. The relative magnitudes of the acid dissociation constants are summarised by Pauling's rules and the speciation of the fully hydrolysed elements in natural waters largely depends on pH and, to a lesser extent, on interactions with the major cations. The remaining cations of low and intermediate polarising power can be subdivided according to their tendency to form covalent bonds. An empirical parameter Δβ(= logβ⁰_MF ? log β⁰_MCl) is used to define (a)-type (Δβ > 2), borderline (a)-type (2 >Δβ > 0), (b)-type (Δβ < ?2) and borderline (b)-type (0 >Δβ > ?2) cations. Again these various categories form coherent groupings on the periodic table. By considering the interactions of cations from the various categories with the inorganic ligands commonly encountered in natural waters it is possible to assign the ligands themselves to ‘hard’ (e.g. F^?, SO₄^2?), ‘intermediate’ (e.g. OH^?, CO^2?₃) and ‘soft’ categories (e.g. Cl^?). These concepts can be summarised by constructing a Complexation Field Diagram in which the various cations are located on a plot of $\text{z}{}^2\text{r}$ vs δβ. The extension of the model to include redox equilibria and additional ligands is described.     

Diversity of Mn oxides produced by Mn(II)-oxidizing fungi

Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four different species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerina strain DS2psM2a2, Pyrenochaeta sp. DS3sAY3a, Stagonospora sp. SRC1lsM3a, and Acremonium strictum strain DS1bioAY4a) isolated from acid mine drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling synthetic δ-MnO₂. The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictum strain DS1bioAY4a) and triclinic birnessite (Stagonospora sp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large differences in the reactivity of the Mn oxide phases.     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.     

Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt - Application to magmatic sulfide deposits

The chalcogenes (S, Se, Te), semimetals (As, Sb) and the metal Bi are important ligands for noble metals and form a wide range of compositionally diverse minerals with the platinum-group elements (PGE). With the exception of S, few experimental data exist to quantify the behavior of these elements in magmatic sulfide systems. Here we report experimental partition coefficients for Se, Te, As, Sb, and Bi between monosulfide solid solution (mss) and sulfide melt, determined at 950 °C at a range of sulfur fugacities (fS2) bracketed by the Fe-FeS (metal-troilite) and the Fe_1−×S-S_x (mss-sulfur) equilibria. Selenium is shown to partition in mss-saturated sulfide melt as an anion replacing S²⁻. Arsenic changes its oxidation state with fS₂ from predominantly anionic speciation at low fS₂, to cationic speciation at high fS₂. The elements Sb, Te, and Bi are so highly incompatible with mss that they can only be present in sulfide melt as cations and/or as neutral metallic species. The partition coefficients derived fall with increasing atomic radius of the element. They also reflect the positions of the respective elements in the Periodic Table: within a group (e.g., As, Sb, Bi) the partition coefficients fall with increasing atomic radius, and within a period the elements of the 15th group are more incompatible with mss than the neighboring elements of the 16th group.     

Dynamics of nutrient elements in three estuaries of North China: The Luanhe, Shuangtaizihe, and Yalujiang

Concentrations of nutrients (NO₃ ^?, NO₂ ^?, NH₄ ⁺, PO₄ ^3?, and dissolved SiO₂) were examined in three North China estuaries—the Luanhe, Shuangtaizihe, and Yalujiang. These riverine-estuarine systems provide distinct geographic and hydrodynamic conditions, that is, a shallow water zone embraced by shoals and sandbars (Luanhe), the confluence of two streams in the upper estuary with different water and sediment loads, and a turbidity maximum in the upper estuarine mixing zone (Yalujiang). Nutrient element concentrations in these rivers are high in comparison with large, less disturbed systems but similar to those from polluted and/or eutrophic European and North American rivers. This is attributed to intensive weathering and erosion and extensive use of chemical fertilizers. In the fresh-marine waters mixing zone, nutrient species can behave either conservatively or nonconservatively, or both. Wherever nonconservative behaviours of nutrient elements are observed, remobilization from solid phases is probably the predominant mechanism. The extrapolation of dilution curves to the fresh water end-members gives estimated riverine concentrations, which can be between two and ten times higher than those from field observations. Taking into account the high N:P ratios (10²–10⁴) from North China rivers and very low concentrations of nitrogen species in the Northwest Pacific coastal oceans (e.g., Yellow Sea), the estuaries in this study may act as regions in which production is limited by phosphorus to regions in which production is limited by nitrogen.     

Biomineralization of As(V)-hydrous ferric oxyhydroxide in microbial mats of an acid-sulfate-chloride geothermal spring, Yellowstone National Park

Acid-sulfate-chloride (pH∼3) geothermal springs in Yellowstone National Park (YNP) often contain Fe(II), As(III), and S(-II) at discharge, providing several electron donors for chemolithotrophic metabolism. The microbial populations inhabiting these environments are inextricably linked with geochemical processes controlling the behavior of As and Fe. Consequently, the objectives of the current study were to (i) characterize Fe-rich microbial mats of an ASC thermal spring, (ii) evaluate the composition and structure of As-rich hydrous ferric oxides (HFO) associated with these mats, and (iii) identify microorganisms that are potentially responsible for mat formation via the oxidation of Fe(II) and or As(III). Aqueous and solid phase mat samples obtained from a spring in Norris Basin, YNP (YNP Thermal Inventory NHSP35) were analyzed using a complement of chemical, microscopic and spectroscopic techniques. In addition, molecular analysis (16S rDNA) was used to identify potentially dominant microbial populations within different mat locations. The biomineralization of As-rich HFO occurs in the presence of nearly equimolar aqueous As(III) and As(V) (∼12 μM), and ∼ 48 μM Fe(II), forming sheaths external to microbial cell walls. These solid phases were found to be poorly ordered nanocrystalline HFO containing mole ratios of As(V):Fe(III) of 0.62 ± 0.02. The bonding environment of As(V) and Fe(III) is consistent with adsorption of arsenate on edge and corner positions of Fe(III)-OH octahedra. Numerous archaeal and bacterial sequences were identified (with no closely related cultured relatives), along with several 16S sequences that are closely related to Acidimicrobium, Thiomonas, Metallosphaera and Marinithermus isolates. Several of these cultured relatives have been implicated in Fe(II) and or As(III) oxidation in other low pH, high Fe, and high As environments (e.g. acid-mine drainage). The unique composition and morphologies of the biomineralized phases may be useful as modern-day analogs for identifying microbial life in past Fe-As rich environments.     

Geological and Palaeontological context of three new Barremian (Lower Cretaceous) vertebrate sites in the Iberian Peninsula (Cuenca Province,Central Spain)

Three new Lower Cretaceous vertebrate sites (Vadillos-1, Vadillos-2, El Tobar) have been recently discovered and studied in the Cuenca Province (Central Spain). They are located in deposits of “Wealden” facies belonging to the El Collado Sandstone and Clay Formation. In these outcrops, micro and macroremains corresponding to plants, invertebrates and vertebrates have been collected and subsequently assigned to macrophytes, charophytes (e.g., Atopochara trivolvis triquetra, Globator maillardii trochiliscoides, Clavator harrisii harrisii), ostracods (e.g., Cypridea gr. modesta, Cypridea cf. C. isasae, Cypridea sp. aff. C. moneta, Cypridea sp. 1, Cypridea sp. 2), molluscs (Unionoida, Viviparus sp.), fishes, amphibians, turtles (cf. Eucryptodira), crocodyliforms (Neosuchia) and dinosaurs (ankylosaurs, ornithopods, theropods). Among the vertebrate remains, scales, teeth, plates, osteoderms, phalanges, ribs, vertebrae and other incomplete bones, as well as eggshell fragments have been identified. This rich and diverse assemblage was deposited in an upper Barremian alluvial-palustrine muddy floodplain crossed by braided sandy channels.     

Numerical evaluation of seismic response of shallow foundation on loose silt and silty sand

This study includes the results of a set of numerical simulations carried out for sands containing plastic/non-plastic fines, and silts with relative densities of approximately 30?40% under different surcharges on the shallow foundation using FLAC 2D. Each model was subjected to three ground motion events, obtained by scaling the amplitude of the El Centro (1940), Kobe (1995) and Kocaeli (1999) Q12earthquakes. Dynamic behaviour of loose deposits underlying shallow foundations is evaluated through fully coupled nonlinear effective stress dynamic analyses. Effects of nonlinear soil structure interaction (SSI) were also considered by using interface elements. This parametric study evaluates the effects of soil type, structure weight, liquefiable soil layer thickness, event parameters (e.g., moment magnitude of earthquake (M _w ), peak ground acceleration PGA, PGV/PGA ratio and the duration of strong motion (D _5?95) and their interactions on the seismic responses. Investigation on the effects of these parameters and their complex interactions can be a valuable tool to gain new insights for improved seismic design and construction.     

Palynofacies patterns of the Devonian of the Parnaíba Basin,Brazil: Paleoenvironmental implications

To help describe the paleoenvironmental interpretation of one the most extensive marine Devonian successions in Brazil, palynofacies analyses were conducted on 46 samples from the Itaim (Pragian–Givetian), Pimenteira (Givetian–Frasnian) and Cabeças (Famennian) formations of the Parnaíba Basin in north–central Brazil. For the palynofacies analyses, kerogen categories were counted and subjected to cluster analyses. Five palynofacies associations were identified for three studied sections: PseudoAOM palynofacies, which consists of amorphous organic matter (AOM), pseudoamorphous and coenobial algae Quadrisporites; Transl/Nbiostr. palynofacies, which consists of translucent non-biostructured phytoclasts (well-preserved and degraded), cuticles (well-preserved and degraded), Spongiophyton and Botryococcus; Marine microplankton palynofacies, which consists of acritarchs, prasinophytes and translucent biostructured phytoclasts; Opaque palynofacies, which consists of opaque phytoclasts (equidimensional and lath shaped); and Sporomorphs palynofacies, which consists of zoomorphs (e.g., Chitinozoa) and sporomorphs (e.g., spores). The stratigraphic distribution of the five palynofacies associations reflects a continuous terrestrial influx throughout marine succession. At the Pragian–Emsian age, the woody material of Transl/Nbioestr. palynofacies prevails, suggesting a marine depositional paleoenvironment (presence of marine palynomorphs), but under deltaic influence due to the input of terrigenous material. An increasing trend of marine elements of Marine microplankton palynofacies is recorded for the Givetian, which suggests a progressive marine influence. However, during the Frasnian, the highest abundance of marine elements was recorded (Marine microplankton palynofacies). Moreover, a bloom of Maranhites spp. and prasinophytes (e.g., Tasmanites and Cymatiosphaera) was also recorded. The abrupt increase of marine palynomorphs in the Frasnian – here termed the “Maranhites Event” – has been recorded by other authors. Finally, in the Famennian, woody material was most abundant in Transl/Nbiostr. palynofacies and Sporomorphs palynofacies, which reflects a depositional trend that is strongly controlled by fluvial input into a shallow marine environment.     

‘Large Igneous Provinces (LIPs)’: Definition,recommended terminology,and a hierarchical classification

This article is an appeal for the adoption of a correct and appropriate terminology with respect to the so-called Large Igneous Provinces (LIPs). The term LIP has been widely applied to large basaltic provinces such as the Deccan Traps, and the term Silicic Large Igneous Province (SLIP) to volcanic provinces of dominantly felsic composition, such as the Whitsunday Province. However, neither term (LIP, SLIP) has been applied to the large granitic batholiths of the world (e.g., Andes) to which both terms are perfectly applicable. LIP has also not been applied to broad areas of contemporaneous basalt magmatism (e.g., Indochina, Mongolia) and sizeable layered mafic intrusions (e.g., Bushveld) which in many significant respects may also be considered to represent ‘Large Igneous Provinces’. Here, I suggest that the term LIP is used in its broadest sense and that it should designate igneous provinces with outcrop areas ≥ 50,000 km². I propose a simple hierarchical classification of LIPs that is independent of composition, tectonic setting, or emplacement mechanism. I suggest that provinces such as the Deccan and Whitsunday provinces should be called Large Volcanic Provinces (LVPs), whereas large intrusive provinces (mafic–ultramafic intrusions, dyke/sill swarms, granitic batholiths) should be called Large Plutonic Provinces (LPPs). LVPs and LPPs thus together cover all LIPs, which can be felsic, mafic, or ultramafic, of sub-alkalic or alkalic affinity, and emplaced in continental or oceanic settings. LVPs are subdivided here into four groups: (i) the dominantly/wholly mafic Large Basaltic Provinces (LBPs) (e.g., Deccan, Ontong Java); (ii) the dominantly felsic Large Rhyolitic Provinces (LRPs) (e.g., Whitsunday, Sierra Madre Occidental); (iii) the dominantly andesitic Large Andesitic Provinces (LAPs) (e.g., Andes, Indonesia, Cascades), and (iv) the bimodal Large Basaltic–Rhyolitic Provinces (LBRPs) (e.g., Snake River–High Lava Plains). The intrusive equivalents of LRPs are the Large Granitic Provinces (LGPs) (e.g., the Andean batholiths), although an equivalent term for intrusive equivalents of LBPs is not necessary or warranted. The accuracy and usefulness of the terms flood basalt, plateau basalt, and trap are also examined. The largest LBP, LVP, and LIP is, of course, the bulk of the ocean floor. It is contended that the proposed LIP nomenclature and classification will lead to more accurate and precise terminology and hence better understanding of the wide variety of Large Igneous Provinces.     

Trace element abundances and mineral/melt distribution coefficients in phonolites from the Laacher See volcano (Germany)

Twenty six whole rocks, seven matrix and fifty three mineral separates from the compositionally zoned late Quaternary Laacher See tephra sequence (East Eifel, W Germany) were analyzed by instrumental neutron activation. These data document the chemical variation within the Laacher See magma chamber prior to eruption with a highly fractionated phonolite at the top and a more mafic phonolite at its base as derived from other data. Incompatible elements such as Zn, Zr, Nb, Hf, U, light and heavy rare earths are extremely enriched towards the top whereas compatible elements (e.g. Sr, Sc, Co, Eu) are strongly depleted. Semicompatible elements (Ta and some middle REE) are depleted at intermediate levels. This chemical variation is shown by whole rock and matrix data indicating the phonolite liquid was compositionally zoned regardless of phenocryst content. Hybrid rocks (phonolite-basanite) show the largest concentrations for compatible elements. All elements (except Rb) display continuous compositional variations with regard to the stratigraphic position of pumice samples. From these data we are able to distinguish three main units: An early erupted highly fractionated magma, the main volume of evolved phonolite and a mafic phonolite as the final products. The extreme variation of trace element distribution coef ficients (K) for 9 mineral phases with respect to stratigraphic position (resp. matrix composition) cannot be explained by conventional mechanisms. We postulate a significant modification of the trace element content of the phonolite melt by liquid-liquid controlled differentiation processes subsequent to and/or contemporaneous with (fractional) crystallization which caused disequilibrium between phenocrysts and host matrix. Therefore, our “distribution coefficients” deviate from equilibrium partition coefficients equivalent to the amount of this post crystallization modification of the matrix composition. The relationship between varying K and matrix composition is demonstrated by a ΔK-ΔM-diagram (variation of K versus variation of matrix, M). Different parts of this diagram relate to different parameters (T, P, polymerization, complex-building, equilibrium crystallization in a zoned magma column and post crystallization disequilibrium effects) which are responsible for the variation of distribution coefficients in general. The ΔK-ΔM-diagram may allow to distinguish between different processes affecting the distribution coefficients measured in natural volcanic rocks from a differentiating magma system.     

Geochronology,geochemistry and petrogenesis of the Laozhaishan dolerite sills in the southeastern margin of the North China Craton and their geological implication

The configuration of the North China craton (NCC) in the Rodinia supercontinent still remains controversial due to few reliable Neoproterozoic magmatism records. Here we report early Neoproterozoic dolerite sill swarms in the Laozhaishan region in the southeastern margin of the NCC. These sills intrude the Neoproterozoic sedimentary rocks (Wangshan, Gouhou and Shijia Formations), and are up to several hundred meters in thickness and >30 km in length. Baddeleyites separated from several representative dolerite samples show SIMS ²⁰⁷Pb-²⁰⁶Pb ages varying from 912 ± 4 Ma to 916 ± 4 Ma, which are consistent with concordant zircons U-Pb age of 913 ± 10 Ma. Geochemically, the Neoproterozoic dolerite samples have relatively low rare earth elements (REEs) contents and show weak positive Eu anomalies. Moreover, these dolerite rocks are enriched in light rare earth elements (LREEs), large ion lithophile elements (LILEs; e.g., Rb and Ba) and some high field strength elements (HFSEs; e.g., Nb, U, Nd, Ti, Gd) and depleted in heavy rare earth elements (HREEs) and several HFSEs (e.g., Zr, Th), with geochemical affinities to within-plate tholeiitic basalts. The REE patterns, whole-rock ε_Nd(t) (t = 913 Ma) values varying from −0.60 to +3.12, and in-situ ε_Hf (t) (t = 913 Ma) values between +4.50 to +12.85 suggest that these dolerites were generated by mantle plumes, in which some enriched components were involved. In the context of assembly, growth and breakup of the Rodinia supercontinent, together with the recognition of ~913 Ma dolerite swarms in the NCC as well as nearly coeval rift-related magmatism recorded elsewhere on the globe such as the Congo craton and the São Francisco craton, we conclude that the NCC has involved in the evolution of Rodinia and the widespread dolerite swarms indicate the breakup of Rodinia.     

Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.     

Microbial community signature in Lake Coeur d’Alene: Association of environmental variables and toxic heavy metal phases

The water and sediments of Lake Coeur d’Alene in northern Idaho (USA) have been impacted by decades of mining operations within the Coeur d’Alene mining district. Using a multivariate statistical approach, correlations were explored between the microbial community (via 16S rDNA microarray) in sediment cores and operationally defined heavy metal phases (via continuous sequential extractions). Candidate phyla NC10, OP8 and LD1PA were only detected in metal contaminated cores and diversity doubled among Natronoanaerobium in metal contaminated cores compared to the uncontaminated control site. This may suggest some increased fitness of these phyla in contaminated sediments. In contrast, diversity within the phyla Aquificae, Coprothermobacteria, and Synergistes was at least double in the uncontaminated control site. In linear models composed of two geochemical variables from the presumed sulfate reducing lineages detected in this study, orders Desulfobacterales, Desulfuromonadales, Desulfotomaculum, and Syntrophobacterales were highly correlated with Pb (positive influence) and Zn (negative influence) in the operationally defined residual fraction, and most taxa within orders from Desulfovibrionales. Bdellovibrionales highly correlated with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. Diversity within families from metal reducing bacterial lineages Shewanellaceae, Geobacteraceae, and Rhodocyclaceae showed high correlation with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. To our knowledge, this is the first time these techniques have been used in combination to describe a contaminated system. Resulting correlations suggest the diversity of the microbial community was influenced primarily by partitioning of heavy metals into exchangeable Pb over other Pb phases and, to a lesser extent, residual Pb to residual Zn phase partitioning.     

On the Relationship between Mantle Metasomatism and Partial Melting-Evidence from Mantlederived Lherzolite Xenoliths from Nueshan,China

Studies of the mantle-derived iherzolites from Nushan show that in addition to CO2,there were present H2O and small amounts of CO, CH4, SO2,Cl and F in the initial mantlc fluids derived fron the asthenospheric mantlc plumc .The imitial fluids accumulated in some regions of the mantle, resulting in lowering of the mantle solidus (and liquidus) and partial melting of the upper mantle. Melts formed from low-degree of fluid-involved partial melting of the upper mantle would be highly enriched in incompatible elements.Fluies and melts are allthe metasomatic agents for mantle metasomatism, and the interaction between them and the depleted mantle could result in the substan-tial local enrichment of LREE and incompatible elements in the latter.In case that the concentration of H2O in the fluids (and melts) is lower ,only cryptic metasomatism would occur, in case that the concentration of H2O is higher,the degree of partial melting would be higher and hydrous metasomatic phases(e.g. amphiboles )would nucleate. Under such circumstances, there would occur model metasomatism.     

Relationship between subcellular cadmium distribution in prey and cadmium trophic transfer to a predator

We tested the hypothesis that exposure-related alterations in the subcellular Cd distribution in prey relate to changes in Cd absorption by a predator. Oligochaete worms,Limnodrilus hoffmeisteri were exposed for 1 wk or 6 wk to 0.5 μg Cd 1^?1, 47 μg Cd 1^?1, or 140 μg Cd 1^?1 (including¹⁰⁹Cd as a tracer) and relationships between oligochaete subcellular Cd distribution and Cd absorption by a predator, the grass shrimp (Palaemonetes pugio), were determined. Concentration and duration of Cd exposure had direct effects on oligochaete subcellular Cd distribution. Changes in oligochaete subcellular Cd distribution were characterized by increases in both the amount and proportion of Cd bound to the cytosolic fraction. The induction of Cd-binding proteins (e.g., metallothioneins) were suspected to be responsible for these changes. We found 1∶1 relationships between the amount and percentage of Cd in oligochaete cytosol and the amount and percentage of Cd adsorbed by shrimp. These results demonstrate that only metal bound to the soluble fraction of prey is available to higher trophic levels, and that factors influencing subcellular metal distribution in prey will directly alter metal trophic transfer to predators.     

Three cubic phases intergrown in a birefringent andradite-grossular garnet and their implications

The crystal chemistry across the garnet series is examined, and several systematic trends are reported. The crystal structure of three different cubic phases intergrown in a birefringent near end-member andradite from Namibia was refined by the Rietveld method, space group $ Ia\bar{3}d, $ Ia 3 ¯ d , and monochromatic synchrotron high-resolution powder X-ray diffraction data. Electron microprobe results indicate three phases with distinct compositions. The sample is birefringent, indicating that it is not cubic when observed optically. The reduced χ ² and overall R (F ²) Rietveld refinement values are 1.655 and 0.0284, respectively, so the multi-phase refinement is excellent. The composition, weight %, unit-cell parameter (Å), distances (Å), and site-occupancy factors (sofs) are as follows: phase-1, Adr₉₉, 88.5(1)  %, a = 12.06259(1), average 〈Ca–O〉 = 2.4310, Fe–O = 2.0189(4), Si–O = 1.6490(4) Å, Ca(sof) = 0.948(1), Fe(sof) = 0.934(1), and Si(sof) = 0.940(1). For phase-2: Adr₇₁Grs₂₈, 7.1(1) %, a = 12.00361(5), average 〈Ca–O〉 = 2.440, Fe–O = 1.979(3), Si–O = 1.641(3) Å, Ca(sof) = 0.913(5), Fe(sof) = 0.767(4), and Si(sof) = 0.932(5). For phase-3: Grs₇₉Adr₁₇, 4.4(1) %, a = 11.89719(4), average 〈Ca–O〉 = 2.404, Al–O = 1.935(4), Si–O = 1.667(3) Å, Ca(sof) = 0.944(6), Al(sof) = 1.069(7), and Si(sof) = 0.887(5). The dominant phase-1 (89 %; Adr₉₉) is nearly end-member andradite, Ca₃Fe ₂ ³⁺ Si₃O₁₂, which contains no cation order in the Ca(X) or Fe(Y) sites. The intergrowth of the three cubic phases causes considerable strain in the minor phases-2 and phases-3 that arise from different structural parameters and gives rise to strain-induced birefringence. For comparison, the results for an isotropic, single-phase, grossular–andradite garnet (Grs₇₆Adr₂₁) are also presented. The strain in the minor phases is about 3–5 times more than the unstrained dominant phase-1, or the unstrained single-phase grossular–andradite.     

Bacterially-mediated weathering of crystalline and amorphous Cu-slags

Two types of Cu-slags (CS: crystalline massive slag and GS: granulated amorphous slag) exhibiting a different chemical and mineral phase composition were compared with respect to their susceptibility to bacterial weathering using Pseudomonas aeruginosa (n° CIP 105094). Abiotic conditions e.g. sterile growth medium and ultrapure water were used for comparison. The experiments were extended up to 112 days with a systematic liquid phase renewal every 14 days. The results revealed significant release of elements in the bacterially mediated weathering experiments. Concentrations of elements (Si, Fe, Cu, Zn and Pb) in the biotic solutions were increased at least by 20% up to 99% compared to abiotic ones. From 3 to 77% of the leached elements were associated to the fraction >0.22 μm. Scanning electron microscope observations demonstrated greater weathering of mineral phases in biotic experiments than in abiotic ones which is in accordance with the solution chemistry exhibiting higher concentrations of elements leached in biotic set-ups. In the case of CS, glass and sulfides weathering was yet observed in abiotic experiment, whereas partial dissolution of fayalite (Fe₂SiO₄) was solely affected by the presence of bacteria. GS having a higher bulk content of metallic elements was found to be more stable than sulfide-bearing CS, while its (GS) glass matrix was found to weather easier under biotic conditions.