Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

Groundwater Resources In Hard Rock; Experiences from The Hvaler Study,Southeastern Norway

Investigations in a newly constructed subsea road tunnel in the Iddefjord granite at Hvaler and test-pumping of boreholes on land indicate that a topographic or geophysical anomaly is no guarantee of a substantially transmissive fracture zone. Many prominent fracture zones appear to have depressed transmissivity due to secondary swelling-clay mineral infillings. No current geophysical technique can adequately distinguish these zones from transmissive ones. Given that siting of boreholes on the basis of geology alone can be unreliable, hydrogeologists should concentrate on quantifying the chances of a successful boring, and optimizing those chances by sensible location, favourable borehole orientation and use of artificial enhancement techniques.     

Genesis and evolution of the lithospheric mantle beneath the Buffalo Head Terrane, Alberta (Canada)

Mantle xenoliths and xenocrysts were retrieved from three of the 88–86 Ma Buffalo Hills kimberlites (K6, K11, K14) for a reconnaissance study of the subcontinental lithospheric mantle (SCLM) beneath the Buffalo Head Terrane (Alberta, Canada). The xenoliths include spinel lherzolites, one garnet spinel lherzolite, garnet harzburgites, one sheared garnet lherzolite and pyroxenites. Pyroxenitic and wehrlitic garnet xenocrysts are derived primarily from the shallow mantle and lherzolitic garnet xenocrysts from the deep mantle. Harzburgite with Ca-saturated garnets is concentrated in a layer between 135–165 km depth. Garnet xenocrysts define a model conductive paleogeotherm corresponding to a heat flow of 38–39 mW/m². The sheared garnet lherzolite lies on an inflection of this geotherm and may constrain the depth of the lithosphere–asthenosphere boundary (LAB) beneath this region to ca 180 km depth.

A loss of >20% partial melt is recorded by spinel lherzolites and up to 60% by the garnet harzburgites, which may be related to lithosphere formation. The mantle was subsequently modified during at least two metasomatic events. An older metasomatic event is evident in incompatible-element enrichments in homogeneous equilibrated garnet and clinopyroxene. Silicate melt metasomatism predominated in the deep lithosphere and led to enrichments in the HFSE with minor enrichments in LREE. Metasomatism by small-volume volatile-rich melts, such as carbonatite, appears to have been more important in the shallow lithosphere and led to enrichments in LREE with minor enrichments in HFSE. An intermediate metasomatic style, possibly a signature of volatile-rich silicate melts, is also recognised. These metasomatic styles may be related through modification of a single melt during progressive interaction with the mantle. This metasomatism is suggested to have occurred during Paleoproterozoic rifting of the Buffalo Head Terrane from the neighbouring Rae Province and may be responsible for the evolution of some samples toward unradiogenic Nd and Hf isotopic compositions.

Disturbed Re–Os isotope systematics, evident in implausible model ages, were obtained in situ for sulfides in several spinel lherzolites and suggest that many sulfides are secondary (metasomatic) or mixtures of primary and secondary sulfides. Sulfide in one peridotite has unradiogenic ¹⁸⁷Os/¹⁸⁸Os and gives a model age of 1.89±0.38 Ga. This age coincides with the inferred emplacement of mafic sheets in the crust and suggests that the melts parental to the intrusions interacted with the lithospheric mantle.

A younger metasomatic event is indicated by the occurrence of sulfide-rich melt patches, unequilibrated mineral compositions and overgrowths on spinel that are Ti-, Cr- and Fe-rich but Zn-poor. Subsequent cooling is recorded by fine exsolution lamellae in the pyroxenes and by arrested mineral reactions.

If the lithosphere beneath the Buffalo Head Terrane was formed in the Archaean, any unambiguous signatures of this ancient origin may have been obliterated during these multiple events.     

Nanoscale study of As biomineralization in an acid mine drainage system

Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoulès (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoulès water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoulès AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L_2,3-edge, and As L_2,3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoulès AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoulès AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments.     

A methodology for locating the original quarries used for constructing historical buildings: application to Málaga Cathedral, Spain

It is often necessary to locate the original quarry which supplied the stone for a particular historical building. This stones could be used for future restoration work and for testing in the laboratory (artificial aging tests, physical properties determination, control of the efficacy of conservation treatments, etc.). Generally, reviewing historical documentation gives information about the geographical setting of quarries and location of the stones in the monument, but this information needs to be proved by field and laboratory studies. The comparative study of stone from quarries and monuments should basically include the following: (1) mineralogical and petrographical studies; (2) the chemical analysis of major, minor and trace elements; (3)stable isotopes determinations; (4) physical properties of quarry materials and unweathered building stone (water absorption, ultrasound transmission velocity, porosity and porous system, density, bulk density, compressive strength, etc.). This methodology was applied to Málaga Cathedral stones represented in the main façade, towers, and the western zone of the terrace, which, according to historical literature, came from Almayate (Miocene–Pliocene limestones) and Cerro Coronado (Permotriassic sandstone) in Málaga. The conclusion of the comparative study carried out on quarries and building stones was consistent with the information available from the historical documentation.     

Andesite and dacite genesis via contrasting processes: the geology and geochemistry of El Valle Volcano,Panama

The easternmost stratovolcano along the Central American arc is El Valle volcano, Panama. Several andesitic and dacitic lava flows, which range in age 5–10 Ma, are termed the old group. After a long period of quiescence (approximately 3.4 Ma), volcanic activity resumed approximately 1.55 Ma with the emplacement of dacitic domes and the deposition of dacitic pyroclastic flows 0.9–0.2 Ma. These are referred to as the young group. All of the samples analyzed are calc-alkaline andesites and dacites. The mineralogy of the two groups is distinct; two pyroxenes occur in the old-group rocks but are commonly absent in the young group. In contrast, amphibole has been found only in the young-group samples. Several disequilibrium features have been observed in the minerals (e.g., oscillatory zoning within clinopyroxenes). These disequilibrium textures appear to be more prevalent among the old- as compared with the young-group samples and are most likely the result of magma-mixing, assimilation, and/or polybaric crystallization. Mass-balance fractionation models for major and trace elements were successful in relating samples from the old group but failed to show a relationship among the young-group rocks or between the old- and young-group volcanics. We believe that the old-group volcanics were derived through differentiation processes from basaltic magmas generated within the mantlewedge. The young group, however, does not appear to be related to more primitive magmas by differentiation. The young-group samples cannot be related by fractionation including realistic amounts of amphibole. Distinctive geochemical features of the young group, including La/Yb ratios〉15, Yb〈1, Sr/Y〉150, and Y〈6, suggest that these rocks were derived from the partial melting of the subducted lithosphere. These characteristics can be explained by the partial melting of a source with residual garnet and amphibole. Dacitic material with the geochemical characteristics of subducted-lithosphere melting is generated apparently only where relatively hot crust is subducted, based on recent work. The young dacite-genesis at El Valle volcano is related to the subduction of relatively hot lithosphere.     

Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Zircon textures and composition: refractory recorders of magmatic volatile evolution?

Zircon textures and composition have been used to infer magmatic processes including closed-system fractional crystallization, magma mixing or replenishment, and country-rock assimilation. Here, we propose that zircon textures and composition may also be refractory recorders of magmatic volatile evolution. We present field, whole-rock chemical, textural, mineral chemical, and U–Pb age data from evolved, fine-to-coarse-grained granite intrusions on Melville Peninsula, Nunavut, Canada. Zircon forms two main populations in these granites, Type-1 and Type-2 zircon. Type-1 zircon is present in all samples, but predominant in fine-grained granite. Crystals are euhedral and inclusion-rich and show periodic, fine-scale oscillatory zoning, comparatively low concentrations of U (<2,200 ppm) and Hf (<1.6 wt%), high Zr/Hf (~40–62), and pervasive alteration. Type-2 zircon is predominant in coarse-grained granite. Crystals form overgrowths on Type-1 zircon and individual crystals. They are subhedral and inclusion-poor and show weak, irregular, large-scale oscillatory zoning, high U (up to ~7,250 ppm) and Hf (1.5–2.0 wt%), low Zr/Hf (~37–44), and only local alteration. Compatible trace-element concentrations and Zr/Hf change sharply across the boundary of Type-1 to Type-2 zircon; ²⁰⁷Pb/²⁰⁶Pb ages preclude a significant hiatus between crystallization of the two types. We argue against magmatic versus hydrothermal crystallization, country-rock assimilation, or magma mixing as causes for the crystallization of Type-1 and Type-2 zircon. We propose instead that Type-1 zircon formed from volatile-undersaturated magmas and that Type-2 zircon formed from volatile-saturated magmas. Magmas fractionated by volatile-driven filter pressing into crystal-rich mush and crystal-poor magma. Crystal-rich mush with abundant Type-1 zircon crystallized to fine-grained granite. Volatile-rich magma crystallized to Type-2 zircon and coarse-grained granite. While Type-1 zircon was pervasively altered by exsolving magmatic volatiles, Type-2 zircon was only locally affected by subsolidus hydrothermal alteration.     

Carbonate deposition in a fluvial tufa system: processes and products (Corvino Valley – southern Italy)

In a multi‐scale approach to the study of the organic and mineral components in an active barrage‐type tufa system of southern Italy, neo‐formed deposits, in both natural depositional sites and on inorganic substrates placed in the stream for this study, were observed and compared through one year of monitoring. Dams and lobes representing the basic morpho‐facies of the deposits are composed of two depositional facies: vacuolar tufa (a mixture of phytoclastic and framestone tufa) and stromatolitic tufa (phytoherm boundstone tufa). Three petrographic components comprise both facies: micrite and microsparite, often forming peloidal to aphanitc, laminar and dendrolitic fabrics, and sparite, which occurs as isolated to coalescent fan‐shaped crystals forming botryoids or continuous crusts. All fabrics occurring in all depositional facies are organized into layers with a more or less well‐developed cyclicity, which has its best expression in stromatolitic lamination. The precipitation of all types of calcite (with Mg 1·0 to 3·2 mole % and Sr 0·5 to 0·8 mole %) takes place more or less constantly during all seasons, in spite of the low saturation state of the water (the saturation index range is 0·75 to 0·89) within the active depositional zone; the latter extends for a few hundred microns through the external surface of the deposit. The active depositional zone has a particular micro‐morphology composed of porous micro‐columns (50 to 150 μm in size), separated by interstitial channels. Mineral precipitation occurs upon both external surfaces and within internal cavities of the micro‐columns, while further point sites of precipitation occur suspended within the masses of cyanobacterial tufts. Sub‐spherical mineral units, ‘nano‐spheres’ (10 to 20 nm in diameter) are the basic biotic neo‐precipitate; they commonly form by replacing non‐living degrading organic matter and at point sites along the external surface of living cyanobacterial sheaths. Nano‐spheres agglutinate to form first rod‐shaped aggregates (100 to 200 nm) which then evolve into triads of fibres or polyhedral structures. Successively, both triads and polyhedral solids coalesce to form larger calcite crystals (mainly tetrahedrons tens of microns in size) that represent the fundamental bricks for the construction of the micro‐columns in the active depositional zone. Precipitation is attributed to the presence of a widespread biofilm that occurs in the active depositional zone; this is composed of a heterogeneous community comprising epilithic and endolithic filamentous cyanobacteria, green algae, unicellular prokaryotes, actinobacteria and fungi, with a variable amount of extracellular polymeric substances. No precipitation takes place where the biofilm is absent, indicating that the biological activities of the biofilm are crucial, with its living organisms and non‐living organic matter. Basic aggregates of neo‐precipitates do not form in association with any one particular type of organic matter substrate, but appear to be related to the seasonal temperature variation: polyhedral micro‐crystals mainly precipitate in the colder season, short triads in the intermediate seasons, and long triads in the warmest conditions. These three basic crystal aggregates have a petrographic counterpart, respectively, in the spar, microspar and micrite.     

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.075-0.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution.