Pb and other ore metals in modern seafloor tectonic environments: Evidence from melt inclusions

Many modern seafloor tectonic environments are host to hydrothermal systems and associated polymetallic sulfide deposits. Metal transport and precipitation are controlled by magmatic processes such as pre-eruptive degassing and the hydrothermal cycle. The original availability of Pb and other ore metals in a given setting is dependent on concentrations in the original magmatic source or additional enrichment processes. We have examined the Pb budget of melt inclusions from nine modern seafloor settings representing back-arcs, mid-ocean ridges and seamounts. Melt inclusions provide information on the characteristics of parental magmas, including insights into metal budgets. Trace element data in melt inclusions hosted in plagioclase, olivine and pyroxene were obtained by laser-ablation inductively-coupled mass-spectrometry.Results from back-arcs emphasize the impact of slab-subduction and dehydration processes on the chemical characteristics of generated magmas. Volatile- and fluid-mobile element-rich melt inclusions at Manus basin and Okinawa trough reflect a robust contribution of elements from the subducting slab as evidenced by relatively low Ce/Pb ratios. At Bransfield strait, on the other hand, melt inclusions are volatile poor, and fluid-mobile element ratios are similar to mid-ocean ridge values indicating little or no contribution from the slab. High Cu concentrations at Manus basin and Okinawa trough can be explained by fluxing of ferric iron from the subducting slab benefiting the production of sulfate over sulfide.Metal budgets for seamounts located on and nearby the axis of mid-ocean ridge segments appear to be independent of any input of mantle plume material. Results from the southern Explorer ridge (strong lower mantle influence, transitional- and enriched-MORBs), Pito and Axial seamounts (moderate lower mantle influence, transitional-MORBs) and a Foundation near-ridge seamount (little to no mantle influence, normal-MORB) show that, despite similar tectonic environments and varying contributions of mantle plume material, Cu, Zn and Pb values do not vary significantly between the enriched and non-enriched magma components of a given setting.     

An investigation of upper mantle heterogeneity beneath the Archaean and Proterozoic crust of western Canada from Lithoprobe controlled-source seismic experiments

Observations of upper mantle reflectivity at numerous locations around the world have been linked to the presence of a heterogeneous distribution of rock types within a broad layer of the upper mantle. This phenomenon is observed in wide-angle reflection data from Lithoprobe's Alberta Basement Transect [the SAREX and Deep Probe experiments of 1995] and Trans-Hudson Orogen Transect [the THoRE experiment of 1993]. SAREX and Deep Probe image the Archaean lithosphere of the Hearne and Wyoming Provinces, whereas THoRE images the Archaean and Proterozoic lithosphere of the Trans-Hudson Orogen and neighbouring areas.Finite-difference synthetic seismograms are used to constrain the position and physical properties of the reflective layer. SAREX/Deep Probe modelling uses a 2-D visco-elastic finite-difference routine; THoRE modelling uses a pseudospectral algorithm. In both cases, the upper mantle is parameterized in terms of two media. One medium is the background matrix; the other is statistically distributed within the first as a series of elliptical bodies. Such a scheme is suitable for modelling: (1) variations in lithology (e.g., a peridotite matrix with eclogite lenses) or (2) variations in rheology (e.g., lenses of increased strain within a less strained background).The synthetic seismograms show that the properties of heterogeneities in the upper mantle do not change significantly between the two Lithoprobe transects. Beneath the Trans-Hudson Orogen in Saskatchewan, the layer is best modelled to lie at depths between 80 and 150 km. Based on observations from perpendicular profiles, anisotropy of the heterogeneities is inferred. Beneath the Precambrian domains of Alberta, 400 km to the west, upper mantle heterogeneities are modelled to occur between depths of 90 and 140 km. In both cases the heterogeneous bodies within the model have cross-sectional lengths of tens of kilometers, vertical thicknesses less than 1 km, and velocity contrasts from the background of − 0.3 to − 0.4 km/s. Based on consistency with complementary data and other results, the heterogeneous layer is inferred to be part of the continental lithosphere and may have formed through lateral flow or deformation within the upper mantle.     

Analysis of small-scale heterogeneity in clastic rocks by using computerized X-ray tomography (CT)

The aim of this study is to recognize the basic clastic rock types on the basis of Hounsfield Units (HUs) by using statistical methods (hypothesis tests, distribution fitting, and confidence intervals). How does this recognition depend on depositional history of samples tested? Does the numerical pattern of HUs obtained from small-scale analyzing of some particular sedimentary structures coincide to the textural expectations of those sedimentary structures? Are the HU values provided by the CT measurements capable of evidencing micro-cycles belonging to a particular depositional history?For testing the numerical recognition, we analyze macroscopically homogeneous argillaceous marl, siltstone and fine sandstone samples with similar depositional background, age, and degree of diagenesis. The preliminary research shows that the Hounsfield Units can identify different sedimentary rocks considerably well. There are significant differences among the confidence intervals belonging to the different rock types. However, there also have been some slight overlaps among them.For analyzing the effects of the depositional processes in case of a particular rock type, samples from channel sandstone, distributary mouth-bar, massive (structureless) sandstone from a delta-fed turbidity fan, and channel sandstone with traction carpet origin from a delta-fed turbidity fan (all coming from Pannonian basin filling series) are used. The results prove again the significant differences in the terms of both confidence intervals and distribution-types; however, some overlapping also occurs.     

Diffusive reequilibration of quartz-hosted silicate melt and fluid inclusions: Are all metal concentrations unmodified?

Experiments were conducted to determine the extent and mechanism by which the composition of quartz-hosted silicate melt inclusions (SMI) and aqueous fluid inclusions (FI) can undergo post-entrapment modification via diffusion. Quartz slabs containing assemblages of SMI and FI were reacted with synthetic HCl bearing and metalliferous aqueous fluids at T = 500-720 °C and P = 150-200 MPa. SMI from the single inclusion assemblages were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and electron probe microanalysis (EPMA) before and after the experiments. Analyses revealed that rapid diffusion of the univalent cations Na⁺, Li⁺, Ag⁺, Cu⁺ and H⁺ occurred through the quartz from the surroundings, resulting in significant changes in the concentrations of these elements in the inclusions. Concentrations of other elements with an effective ionic radius larger than that of Ag⁺, or multiple valence states were not modified in the inclusions during the experiments. Our results warn inclusion‘‘ researchers that the interpretation of Na, Li, Cu and Ag concentrations from quartz-hosted SMI and FI should be treated critically.     

Diurnal variations in,and influences on,concentrations of particulate and dissolved arsenic and metals in the mildly alkaline Wallkill River,New Jersey,USA

Diurnal variations in particulate and dissolved As and metal concentrations were observed in mildly alkaline water from a wetlands site on the Wallkill River in northwestern New Jersey. The site, underlain by glacial sediments over dolomite bedrock, is 10 km downstream from a mined area of the Franklin Marble, host to Zn ores, also As and Mn minerals. In mid-September 2005, maxima and minima in dissolved-oxygen-concentration and pH, typically caused by photosynthesis and respiration, occurred at 2000 and 0800 hours. Concentrations of dissolved As (1.52–1.95 μg/L) peaked at dusk (2000 hours), whereas dissolved Mn and Zn concentrations (76.5–96.9 and 8.55–12.8 μg/L, respectively) were lowest at dusk and peaked at 1000 hours. These opposing cycles probably reflect sorption and desorption of As (an anion), and Mn and Zn (cations) as pH varied throughout the 24-h period. Doubly-peaked cycles of B, Cl, SO₄, and nutrients also were observed; these may result from upstream discharges of septic-system effluent. Both recoverable amd particulate Al, Fe, Mn, and Zn concentrations peaked between 0200 and 0600 hours. The particulate metals cycle, with perturbations at 0400 hours, may be influenced by biological activity.     

The Kinetics of the Interaction Between Iron(III)-Ethylenediaminetetraacetate and Peroxynitrite

The kinetics of the formation of the purple-colored species between Fe^III-EDTA and peroxynitrite were studied as a function of pH (10.4–12.3) at 22°C in aqueous solutions using a stopped-flow technique. A purple-colored species was immediately formed upon mixing, which had an absorbance maximum at 520 nm. The increase in absorbance with time could be fit empirically by a power function with two parameters a and b. The power equation determined was absorbance = a*t ^b , where a increased linearly with pH and the concentration of peroxynitrite, while b almost remained constant with a value of ~0.25. The molar extinction coefficient ε_520 nm for the colored species was determined as 13 M⁻¹cm⁻¹, which is much lower than ε_520 nm = 520 M⁻¹ cm⁻¹ for the [Fe^III(EDTA)O₂]³⁻, a purple species observed in the Fe^III–EDTA–H₂O₂ system. The results of kinetics and spectral measurements of the present study are briefly discussed and compared with those of the reaction between Fe(III)-EDTA and hydrogen peroxide.     

Strong, localised country-rock contamination and partial homogenisation of a mafic magma: An example from west central Sweden

A dolerite sill cutting slightly older basalt in west-central Sweden shows a strong chemical variation (54% < SiO₂ < 73%) within a restricted area (< 100 × 100 m²). The linear correlation among almost all elements is extremely high; in addition, _NdT is strongly correlated with the SiO₂ content. Least-square hyperbolic-ratio and three-element ratio modelling (common denominator) suggests that most of the chemical variation is explained by mixing and/or micro-mingling. In all, we test 407 hyperbolas, of which 402 are fitted. The five ratio pairs, which could not be fitted to a hyperbola using a least-square fitting procedure, have the ratio Th / Eu in common. Testing the goodness of fit is problematic for hyperbolic distributions; for comparing purposes we sum the distances to chords approximating the hyperbola. Mobile and immobile elements behave similarly, suggesting that no elements are lost or added from outside the system. The data suggests that already the most mafic of the analysed rocks is a mixture of the ‘normal’ dolerite and a siliceous crustal rock. A mafic magma intruded into the base of the crust, where it fractionated resulting in a decreased Mg number. The magma was then contaminated with country rocks in an intermediate magma chamber due to country rock melting; during mixing/mingling almost no fractionation took place. The contaminated rock suggests the presence of a fluid phase. This was probably a prerequisite for country-rock melting. Enrichment in some incompatible elements suggests that besides major mixing/mingling a thermochemical separation process has affected the most felsic rock enriching it in light rare earths and Zr.