Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

Monitoring a Marine Coastal Area: Use of Mytilus galloprovincialis and Mullus barbatus as Bioindicators

Abstract. Samples of Mytilus galloprovincialis and Mullus barbatus were collected in eight coastal sites along the South Adriatic and Ionic coasts of Italy in spring 2000 for a survey of coastal pollution in the Mediterranean basin. Specimens were analysed using an integrated approach based on residue analysis of common aquatic pollutants like organochlorines such as hexachlorobenzene (HCB), DDTs and polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), heavy metals and nonylphenols (NPnE) and biomarker responses such as acetylcholinesterase (AChE) activity, and the two specific P450 activities benzo(a)pyrene monooxygenase (BPMO) and 7-ethoxyre-sorufin-(9-deethylase (EROD). Biological and morphological parameters like somatic liver index (SLI), gonadosomatic index (GSI) and gonadal and gamete histology (eggs and sperms) were also evaluated in red mullet samples. A contamination gradient in which several hot spots occur were revealed in this study. The hot spots account for high levels of organochlorines in both species near incinerators and of PAHs in harbour areas. Levels of both NPnE and AChE activity were highest in two protected marine areas and were within detectable limits in others. This finding was confirmed by P450 activities, in which maximum levels were detected in harbours and protected marine areas. No morphological alterations of male and female gonads were observed on the histological level.     

Multivariate Analysis of an LA-ICP-MS Trace Element Dataset for Pyrite

Application of multivariate statistics to trace element datasets is reviewed using 164 multi-element LA-ICP-MS spot analyses of pyrite from the Moonlight epithermal gold prospect, Queensland, Australia. Multivariate analysis of variance (MANOVA) is used to demonstrate that classification of pyrite on morphological and other non-numeric factors is geochemically valid. Parallel coordinate plots and correlation cluster analysis using Spearman??s coefficients are used to discover unexpected elemental relationships without making assumptions a priori. Finally, principal component analysis and factor analysis are used to demonstrate the presence of sub-classes of pyrite. Corroborated with geological data, statistical analysis provides evidence for successive generations of hydrothermal fluids, each introducing specific metals, and for partial or complete replacement of different minerals. The data permit reinterpretation of Moonlight as a telescoped system where epithermal-Au (± base metals) is superposed onto early porphyry-Mo mineralization.     

Magnetic changes observed in the formation of two filaments in a complex active region: TRACE and MSDP observations

This paper is focused on the formation of two filaments in a complex center of decaying active regions (AR 8329 and AR 8326), located in the northern hemisphere. The observations were obtained in Hα by the Multi-channel Subtractive Double Pass spectrograph (MSDP mounted on the German telescope VTT in Tenerife) and EUV lines with TRACE (Transition Region And Corona Explorer). High Doppler shifts are found to be related to the ends of filament segments where canceling magnetic fields are also located (as seen on magnetograms from Big Bear Solar Observatory). At these locations, velocities along the line of sight, derived by using a cloud model method reach −20 km s⁻¹, the segments of filaments merge and frequently a time-related sub-flare is observed by TRACE. The chirality of the filament segments has been determined by different methods: the segments of dextral chirality join together and form a long dextral filament, and a single filament of sinistral chirality forms end to end with the dextral filament but does not merge with it. Assuming a model of twisted flux tube for filament material, we suggest that the dextral filament has negative helicity and a relationship between its formation and the close by sunspot with the same sign of helicity.     

Minor and trace elements in bornite and associated Cu-(Fe)-sulfides: A LA-ICP-MS studyBornite mineral chemistry

In situ laser ablation inductively-coupled mass spectroscopy (LA-ICP-MS) has been used to provide a baseline dataset on the minor element contents in hypogene bornite and accompanying Cu-sulfides from 12 deposits with emphasis on syn-metamorphic Cu-vein systems in Norway, and skarn, porphyry and epithermal systems in SE Europe.Bornite contains significant concentrations of both Ag and Bi, especially in the vein and skarn deposits studied and has the potential to be a major Ag-carrier in such ores. Concentrations of up to >1 wt.% of both elements are documented. Measured concentrations appear to be independent of whether discrete Ag- and/or Bi-minerals are present within the analyzed sulfide. Where bornite and chalcocite (or mixtures of Cu-sulfides) coexist, Ag is preferentially partitioned into chalcocite over co-existing bornite and Bi is partitioned into the bornite. Bornite is a relatively poor host for Au, which mimics Ag by being typically richer in coexisting chalcocite. Most anomalous Au concentrations in bornite can be readily tracked to micron- and submicron-scale inclusions, but bornite and chalcocite containing up to 3 and 28 ppm Au in solid solution can be documented. Selenium and Te concentrations in bornite may be as high as several thousand ppm and correlate with the abundance of selenides and tellurides within the sample. Selenium distributions show some promise as a vector in exploration, offering the possibility to track a fluid source. Bornite and chalcocite are poor hosts for a range of other elements such as Co, Ni, Ga and Ge, etc. which have been reported to be commonly substituted within sulfides. Hypogene bornite and chalcocite may have significantly different trace element geochemical signatures from secondary (supergene) bornite.     

Simplified Wave Models Applicability to Shallow Mud Flows Modeled as Power-Law Fluids

Simplified wave models- such as kinematic,diffusion and quasi-steady- are widely employed as a convenient replacement of the full dynamic one in the analysis of unsteady open-channel flows,and especially for flood routing.While their use may guarantee a significant reduction of the computational effort,it is mandatory to define the conditions in which they may be confidently applied.The present paper investigates the applicability conditions of the kinematic,diffusion and quasisteady dynamic shallow wave models for mud flows of power-law fluids.The power-law model describes in an adequate and convenient way fluids that at low shear rates fluids do not posses yield stress,such as clay or kaolin suspensions,which are frequently encountered in Chinese rivers.In the framework of a linear analysis,the propagation characteristics of a periodic perturbation of an initial steady uniform flow predicted by the simplified models are compared with those of the full dynamic one.Based on this comparison,applicability criteria for the different wave approximations for mud flood of power-law fluids are derived.The presented results provide guidelines for selecting the appropriate approximation for a given flow problem,and therefore they may represent a useful tool for engineering predictions.     

Perfluorinated compounds in blood of Caretta caretta from the Mediterranean Sea

Perfluorinated compounds (PFCs), widely used for their hydro-oil repellent properties, are almost non-degradable in the environment; there is scientific evidence that indicate bioaccumulation. They represent a threat to many organisms, because they are toxic and are endocrine disruptors. Scientific studies have demonstrated the presence of PFCs in blood and liver samples of fish, turtles, birds and mammals of marine ecosystems in different geographical areas. The aim of this study was to determine the distribution of PFOS and PFOA in blood samples of the marine turtle Caretta caretta, using a minimally invasive sampling procedure. 49 blood samples of marine turtle, taken from several Italian marine turtle rescue centers, were analyzed. While PFOA was never detected, measurable concentrations of PFOS were found in 15 blood samples; the values show a range from 1.14 ng/g to 28.51 ng/g (wet wt.). No differences between groups of samples taken from different areas were found.     

Skarn textures and a case study: the Ocna de Fier-Dognecea orefield, Banat, Romania

We address the question of the predictability of skarn textures and their role in understanding the evolution of a skarn system. Recent models of skarn formation show that skarns are ideal for application of self-organisation theory, with self-patterning the rule in fluid-rock interaction systems rather than the exception. Zonation in skarn deposits, a consequence of infiltration-driven metasomatism, can also be treated in terms of self-organisation. Other less commonly described features, such as scalloping, fingering and mineral banding, can be understood by application of reactive infiltration and hydrodynamics at the skarn front. Devolatilisation may trigger formation of back-flow fluxes that overprint previously formed skarn. The range of textures formed from such events can be used to discriminate between prograde and retrograde stages. Refractory minerals, such as garnet, magnetite and pyrite, readily retain overprinting events. Skarns are also composed largely of minerals from solid solution series (garnet, pyroxene, pyroxenoids, etc.) and therefore skarn mineralogy helps to establish trends of zonation and evolution. The same minerals can act as ‘chemical oscillators’ and record metasomatic trends.The Ocna de Fier-Dognecea deposit was formed in a 10 km deep skarn system. Zonation and evolution trends therefore represent only the result of interaction between magmatically derived fluids emerging at the source and limestone. From the same reason, the transition from prograde to retrograde regime is not influenced by interaction with external fluids. Thirdly, the mineralisation comprises Fe, Cu and Zn-Pb ores, thus facilitating comparison with skarn deposits that commonly are formed in shallower magmatic-hydrothermal environment. Copper-iron ores (magnetite+Cu-Fe sulphides), hosted by magnesian (forsterite+diopside) skarn, occur in the deepest and central part of the orefield, at Simon Iuda. Their petrological character allows interpretation as the core of the skarn system formed from a unique source of fluids emerging from the subjacent granodiorite. It formed first as a consequence of the local setting, where a limestone indented in the granodiorite permitted strong reaction at 650 °C and focussed the up-streaming, buoyant fluids. The first sharp front of reaction is seen at the boundary between the Cu-Fe core and Fe ores hosted by calcic skarn (Di_70-90-And_70-90), where Cu-Fe sulphides disappear, and forsterite gives way to garnet in the presence of diopside (Di₉₀). Following formation of forsterite, devolatilisation and transient plume collapse is interpreted from a range of piercing clusters and trails. We presume lateral flow to have been initiated at the source, as the emerging fluids are in excess to the fluids driven into reaction by the plume. Formation of the other orebodies, up to 5 km laterally downstream in both directions, is interpreted as skarn fingering at the limestone side. The metasomatic front is perpendicular to the flow along the channel of schists placed between the limestone base and the granodiorite.A metal zonation centred onto the source is defined, based on metal distribution: Cu-Fe/Fe/Zn-Pb. The second front of reaction, at the boundary between the Fe and Zn-Pb zone, has a sulphidation/oxidation character, with diopside giving way to a Fe-Mn-rich pyroxene, (HedJoh)_>60+pyroxmangite±bustamite; garnet is minor. Johannsenite-rich pyroxene (Di_20-40Hed_20-40Joh₄₀) is found in proximal skarn at the upper part of Simon Iuda, stable with Zn_0.95Fe_0.05S, at an inferred 570 °C. In distal skarn from Dognecea and Paulus, Mn-hedenbergite (Di_<10Hed₇₀Joh_20-30) formed at 400 °C is stable with Zn_0.84Fe_0.16S. Extensive compositional fields, eutectic decomposition and lamellar intergrowths characterise pyroxene in the Zn-Pb zone, formed at the magnetite-hematite buffer in the presence of pyrite. Distal skarn has a reducing character, in comparison with the proximal. A drop in both fS₂ and O₂, with the zoned system moving closer to the pyrite-pyrrhotite buffer, is induced from the temperature gradient. Based on pyroxene mineralogy and calculated fS₂, the metal zonation is confirmed as being formed upwards and outwards from the source.The Fe and Zn-Pb zones both have a patterned side coexisting with the unpatterned one. Patterning is seen at scales from macroscopic (rhythmic banding, nodular, spotted, orbicular, mossy, mottled textures) to microscopic scales (oscillatory zonation in garnet and silica-bearing magnetite). Following plume updraft, the path of decarbonation reaction controlled the motion of the skarn front until, towards the end of the prograde stage, a multiple steady state regime developed and produced rhythmic patterns on all scales. The activation of powerful patterning operators, represented by Liesegang banding alone, or coupled with competitive particle growth, show that the skarn front had the characteristics of an unstable coarsening front of reaction.A second retrograde event, carbofracturing, triggered by erratic decarbonation after cessation of infiltration, can be interpreted from overprinting textures in the Fe and Zn-Pb zone. A major drop in fO₂ is inferred from extensive, pseudomorphous replacement of hematite by magnetite. Textures show progressive destruction of prograde assemblages, i.e., piercing clusters, shock-induced, fluid-pressure assisted brecciation and deformation, followed by healing of the disrupted assemblages. Release of trace elements accompanies both retrograde events, with a Bi-Te-Au-Ag association common to both. The importance of shock-induced textures is emphasised in the context of Au enrichment, especially when the retrograde fluids cross the main buffers in fO₂-fS₂ space.The presence of Bi-sulphosalt polysomes in the Fe zone indicates that patterning extends down to the nanoscale. The key role played by polysomatism in stabilising compositional trends that cannot otherwise be formed at equilibrium is a fertile ground yet to be adequately explored.     

The Niujiaotang Cd-rich zinc deposit,Duyun, Guizhou province,southwest China: ore genesis and mechanisms of cadmium concentration

The Niujiaotang zinc deposit in southeastern Guizhou, China, is a Mississippi Valley-type Zn deposit within Early Cambrian carbonate rocks. Sphalerite is enriched in cadmium (average 1.4 wt.% Cd), which occurs mostly as isomorphous impurities in the sphalerite lattice. Discrete cadmium minerals (greenockite and otavite) are rare and are found almost exclusively in the oxidation zone of the deposit, probably formed as secondary minerals during weathering–leaching processes. Geochemical data show that the sulfides are enriched in heavy sulfur, with δ³⁴S ranging from +10.0‰ to +32.8‰ (mean +22.5‰). The consistent Pb isotopic compositions in different sulfide minerals are similar to that of Cambrian strata. The ore lead probably came from U- and Th-rich upper crustal rocks, such as the Lower Cambrian Wuxun Formation. The ore fluid is of low-temperature (101°C to 142°C) type, with a Na–Ca–Mg–Cl-dominant composition, and is interpreted as oil-field brine. The data indicate that the metals were mainly derived from the Early Cambrian strata (Qingxudong and Wuxun Formations), whereas sulfur is sourced from sulfate in Cambrian strata or oil-field brines of the Majiang petroleum paleoreservoir. The genetic model for the deposit invokes an Early Cambrian shallow-sea environment on the Yangtze Platform. Zinc and Cd in seawater were concentrated in abundant algae via unknown biological mechanisms, resulting in large amounts of Zn- and Cd-rich algal ooliths. During the Ordovician, concurrent with destruction of the Majiang petroleum paleoreservoir, oil-field brines migrated from the center of the basin to the margin leaching metals from the Cambrian strata. In the Niujiaotang area, preexisting Zn and Cd, particularly in the Qingxudong and Wuxun Formation, were further mobilized by hot brines rising along the Zaolou fault system, forming stratiform and generally conformable Zn–Cd orebodies in reactive carbonate lithologies.