Geology of the volcanic-hosted Brockman rare-metals deposit,Halls Creek Mobile Zone,northwest Australia. l. Volcanic environment,geochronology and petrography of the Brockman volcanics

Summary Rare-metals mineralization of the Brockman deposit (Halls Creek Mobile Zone, NW Australia) is hosted in a fluorite-bearing, rhyolitic volcaniclastic unit informally termed the Niobium Tuff. The Tuff, more correctly described as a tuffaceous volcaniclastic deposit, is the lowermost unit of a sequence of trachyte-to-rhyolite lavas, trachyandesite subvolcanic rocks, and volcaniclastic units of the Brockman volcanics located within the Halls Creek Group, a thick, early Proterozoic volcano-sedimentary sequence. High precision SHRIMP ion-microprobe zircon dating of the Niobium Tuff gives an eruption age of 1870 ± 4 Ma. Regional geochronological constraints indicate the Niobium Tuff was deposited about 15 Ma before major orogenic activity affected the area. Despite folding, faulting and low-grade metamorphism, the Brockman volcanics show excellent preservation of primary volcanological features, including pillow-lavas and pillow-breccias, that suggest a dominantly subaqueous, below-wave-base emplacement environment. The style of eruption products and magma volume constraints suggest the trachyte-dominated volcanics were erupted from a small shield volcanic complex probably in a rift-related basin in a shallow-marine setting. The tectonic setting was intraplate but differs from most Tertiary to recent trachyte volcanic complexes which are largely subaerial, are built on relatively thick continental crust, and show no post-eruptive orogenic history. Brockman-style rare-metal deposits are characterized by preservation of subaqueous volcanics beneath a thick sedimentary sequence, eruption of early incompatible-element enriched products followed by less differentiated magmas, and fine-grained mineralogy influenced by alteration processes. Prospects exist for discovery of analogous deposits, particularly in early Proterozoic mobile belts and Tertiary intraplate shield volcanic provinces.

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Geologie der an Vulkanite gebundenen Seltene-Metalle-Lagerstätte Brockman, Halls Creek Mobile Zone, Nordwest-Australien. I. Vulkanologie, Geochronologie und Petrographie der Brockman-Vulkanite

Zusammenfassung Selten-Metall-Vererzung der Brockman-Lagerstätten (Halls Creek Mobile Zone, NW Australien) sitzt in einer Fluorit-führenden, rhyolitischen vulkanoklastischen Einheit auf, die informell als der Niob-Tuff bezeichnet wird. Es handelt sich hier um ein vulkanoklastisches Tuff-Sediment; dieses ist die unterste Einheit einer Abfolge vor Trachyt bis Rhyolit-Laven, trachyandesitischen Subvulkaniten and vulkanoklastischen Einheiten der Brockman Vulkanite innerhalb der Halls Creek Gruppe, einer mächtigen frühproterozoischen vulkanosedimentdren Abfolge. Prüzisionsdatierungen des Niob Tuffs mit der SHRIMP Ionen-Mikrosonde ergeben ein Eruptionsalter von 1870 +-4 Millionen Jahren. Regionale geochronologische Zusammenhänge zeigen, daß der Niob Tuff etwa 15 Millionen Jahre vor einer größeren Orogenese, die das Gebiet betroffen hat, abgelagert wurde. Trotz Faltung, Bruchtektonik and niedriggradiger Metamorphose zeigen die Brockman-Vulkanite einen hervorragenden Erhaltungszustand primärer vulkanologischer Erscheinungen. Diese urnfassen auch Kissenlaven und KissenBreckzien, die eine vorwiegend subaquatische Ablagerung in ruhigem Wasser erkennen lassen. Die Art der Eruptionsprodukte and das Magmavolumen zeigen, daß die Trachytdominierten Vulkanite von einem kleinen Schildvulkan stammer, wahrscheinlich in einem Becken in einer Rift-Situation im seichten marinen Milieu. Die tektonische Situation war intraplate, aber unterscheidet sich von den meisten tertiären bis rezenten trachytischen Vulkan-Komplexen, die hauptsächlich subaerisch sind, auf einer relativ mächtigen kontinentalen Kruste aufsitzen, and keine post-eruptive orogene Entwicklung zeigen. Seltene-Metalle-Lagerstatten des Brockman-Typs rind durch die Erhaltung subaquatischer-Vulkanite unterhalb einer machtigen sedimentdren Abfolge gekennzeichnet; welters durch frühe Eruptionsprodukte, die an inkompatiblen Elementen angereichert sind, auf die dann weniger differenzierte Magmen folgten, und schließlich durch einen feinkörnigen Mineralbestand, der vor Umwandlungsprozessen betroffen war. Es besteht die Möglichkeit der Entdeckung analoger Lagerstätten, besonders in frühproterozoischen mobilen Gürteln und in tertidren intraplate Schildvulkan Provinzen.

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The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Geochemistry of overbank and high-order stream sediments in Belgium and Luxembourg: a way to assess environmental pollution

A geochemical survey of Belgium and Luxembourg was carried out as part of an international research project entitled ‘Regional geochemical mapping of Western Europe towards the year 2000'. The aim of this research was to map regional background geochemical patterns based on pristine or at least pre-industrial overbank samples and to deduce regional information on the degree of environmental pollution of floodplain and present-day river sediments. Over the entire study area (about 33,000 km²), 66 overbank sites have been sampled. Catchment areas range between 60 and 600 km². At each site an overbank profile has been dug out in the immediate vicinity of the river and described in detail. A first composite sample was taken 5–25 cm below the surface. This sample is supposed to represent deposition over the last centuries. Human interferences in this interval are often inferable based on changed sedimentary characteristics and the presence of anthropogenic particles such as charcoal, slags and brick fragments. A second composite sample was taken at depth, usually >1.5 m below the surface over an interval of about 20 cm. In most sites, the profile characteristics allowed to assume pre-industrial or even pristine conditions for this lower overbank sample. In some profiles this was confirmed by ¹⁴C-dating and/or by the absence of anthropogenic particles. Finally, a present-day stream sediment was sampled on the site to infer the actual pollution status. After drying at 80°C, disaggregation and sieving, the <125 μm fractions of the three sediment samples were analysed by XRF for major elements and several trace elements. Lower overbank samples generally show a direct link with the geological substrate and allow to assess natural background concentrations. Results from the mapping exercise as well as from the statistical analyses display a clear contrast between the northern part of Belgium where Cenozoic unconsolidated sandy and silty formations dominate which are especially vulnerable for erosion, and the southern part of Belgium and Luxembourg where Paleozoic and Mesozoic sandstones, carbonates, marls and shales are the prevalent lithologies. Here the shales are the most intensively eroded lithologies. This is especially reflected in the element patterns of Al₂O₃, MgO, K₂O, Ga, Ni, Rb, Sc and V which negatively correlate with SiO₂. Despite the human related pollution, the geological contrast between north and south Belgium is still recognisable in the geochemical pattern of the upper overbank and present-day stream sediment samples for the above-mentioned elements. Furthermore there is a clear increase in heavy metal contents (Zn, Cd, Pb, Cu), As and in certain locations in Ba from the lower to the upper overbank sediment, as well as to the present-day stream sediment. The relative increase in element content allows to assess the degree of pollution and helps to define those drainage areas where more detailed research is needed.     

Debris flow deposits of early miocene age,deadman stream,Marlborough, New Zealand

Detailed analysis is presented of a conformable succession of Early Miocene conglomerates and sandstones lying between massive marine mudstones. The coarse sediments reflect deposition by a spectrum of subaqueous debris-flow mechanisms during an early pulse of tectonism that ultimately resulted in Plio-Pleistocene eversion of the Kaikoura Mountains.Sparse pebbly mudstones and rare sandy conglomerates show disoriented clasts and reflect high-viscosity flows and slurry-creep flow mechanisms. Other deposits have little mud matrix, hence appear to reflect low-viscosity flow processes. The largest clasts in these have a preferred planar orientation, probably reflecting dispersive grain pressure, and a preferred long-axis orientation parallel to flow direction. Common sorted sandstones and some conglomeratic sandstones show diffuse parallel lamination; with rare exceptions neither grading nor traction structures are present. Other conglomeratic sandstones show trough cross-bedding which we attribute to entrained bedload movement during intersurge episodes of debris flow.Microfossil data from the mudstones indicate sedimentation in an environment of outer neritic to upper bathyal aspect. Most detritus is abraded, suggesting derivation from terrestrial or inner neritic sources, but angular calcilutitic clasts and irregular sandstone and mudstone clasts and rafts were probably derived from submarine erosion between the emergent source area and the site of accumulation. Deposits generally appear to infill broad shallow channels. Paleocurrent and fabric analysis indicate a markedly uniform flow direction throughout succession, and suggest that the locus of channeling remained relatively fixed in space throughout accumulation of hundreds of metres of superimposed, commonly amalgamated debris-flow deposits. Although lateral control away from the measured sequence is limited, we infer that the locus of deposition lay shoreward of any submarine canyon or fan.     

Effects of water-borne copper on metallothionein and lipid peroxidation in the marine amphipod Gammarus locusta

The aim of the current work was to determine over 10 days the effects of water-borne exposure of the marine amphipod Gammarus locusta to 4 microgCu l(-1) on the metallothionein (MT; measured by differential pulse polarography) protection system and lipid peroxidation (LP: thiobarbituric acid-reactive malondialdehyde equivalents) as a measure of oxidative damage. MT levels in exposed animals increased significantly at day 2 (36% > control; P < 0.001) and remained high at days 6 and 10 (55 and 38%, respectively, P < 0.001). The maximum level of MT at day 6 coincided with the highest Cu body-burden. LP increased within I day of exposure, indicative of Cu as an oxidative stressor. However, in contrast to MT, the highest LP level was seen at day 4 (68% > control, P < 0.001) before returning to control values by day 6, indicating a protective role of MT against the pro-oxidant effects of Cu.     

Estuary/ocean exchange and tidal mixing in a Gulf of Maine Estuary: A Lagrangian modeling study

A Lagrangian particle method embedded within a 2-D finite element code, is used to study the transport and ocean–estuary exchange processes in the well-mixed Great Bay Estuarine System in New Hampshire, USA. The 2-D finite element model, driven by residual, semi-diurnal and diurnal tidal constituents, includes the effects of wetting and drying of estuarine mud flats through the use of a porous medium transport module. The particle method includes tidal advection, plus a random walk model in the horizontal that simulates sub-grid scale turbulent transport processes. Our approach involves instantaneous, massive [O(500,000)] particle releases that enable the quantification of ocean–estuary and inter-bay exchanges in a Markovian framework. The effects of the release time, spring–neap cycle, riverine discharge and diffusion strength on the intra-estuary and estuary–ocean exchange are also investigated.The results show a rather dynamic interaction between the ocean and the estuary with a fraction of the exiting particles being caught up in the Gulf of Maine Coastal Current and swept away. Three somewhat different estimates of estuarine residence time are calculated to provide complementary views of estuary flushing. Maps of residence time versus release location uncover a strong spatial dependency of residence time within the estuary that has very important ramifications for local water quality. Simulations with and without the turbulent random walk show that the combined effect of advective shear and turbulent diffusion is very effective at spreading particles throughout the estuary relatively quickly, even at low (1 m²/s) diffusivity. The results presented here show that a first-order Markov Chain approach has applicability and a high potential for improving our understanding of the mixing processes in estuaries.     

Sample treatment with focused ultrasound and bath sonication as a powerful tool for the evaluation of cadmium pollution in estuarine waters

A new sample treatment was developed for the determination of dissolved cadmium in Tagus estuarine waters, based on focused ultrasound in conjunction with small volumes in the extraction steps for Cd pre-concentration. Cadmium was first pre-concentrated using a classical approach (APDC as the complexing agent and MIBK as the organic phase) and then back-extracted into HNO₃ with the aid of focused ultrasound, which reduced the acid concentration by more than one order of magnitude (from 4 to 0.1 mol L^− 3). This sample treatment was accomplished in less than 5 min, using low sample volume (20 mL), and low-volume, low-concentration reagents. The pre-concentration factor used in this work was 25, but different sample/organic volume ratios may be used in order to increase that value. The limit of detection and the limit of quantification in Tagus water samples were 0.03 nmol L^− 1 and 0.1 nmol L^− 3, respectively. Recoveries from spiked Tagus water were higher than 90%. The procedure was validated using the reference estuarine water NRC-SLEW-3. In the solubilization of Cd particulate, bath ultrasonication was used in conjunction with HNO₃ + HCl, followed by H₂O₂, which took about 2 instead of the usual 12 h (cooling included) when high-pressure microwave digestion is used.     

Silica-merrihueite/roedderite-bearing chondrules and clasts in ordinary chondrites: New occurrences and possible origin

Abstract Merrihueite (K,Na)₂(Fe, Mg)₅Si₁₂O₃₀ (na < 0.5, fe > 0.5, where na = Na/(Na + K), fe = Fe/(Fe + Mg) in atomic ratio) is a rare mineral described only in several chondrules and irregularly-shaped fragments in the Mezö-Madaras L3 chondrite (Dodd et al., 1965; Wood and Holmberg, 1994). Roedderite (Na,K)₂(Mg, Fe)₅Si₁₂O₃₀ (na > 0.5, fe < 0.5) has been found only in enstatite chondrites and in the reduced, subchondritic silicate inclusions in IAB irons (Fuchs, 1966; Rambaldi et al., 1984; Olsen, 1967). We describe silica-roedderite-bearing clasts in L/LL3.5 ALHA77011 and LL3.7 ALHA77278, a silica-roedderite-bearing chondrule in L3 Mezö-Madaras, and a silica-merrihueite-bearing chondrule in L/LL3.5 ALHA77115. The findings of merrihueite and roedderite in ALHA77011, ALHA77115, ALHA77278 and Mezö-Madaras fill the compositional gap between previously described roedderite in enstatite chondrites and silicate inclusions in IAB irons and merrihueite in Mezö-Madaras, suggesting that there is a complete solid solution of roedderite and merrihueite in meteorites. We infer that the silica- and merrihueite/roedderite-bearing chondrules and clasts experienced a complex formational history including: (a) fractional condensation in the solar nebula that produced Si-rich and Al-poor precursors, (b) melting of fractionated nebular solids resulting in the formation of silica-pyroxene chondrules, (c) in some cases, fragmentation in the nebula or on a parent body, (d) reaction of silica with alkali-rich gas that formed merrihueite/roedderite on a parent body, (e) formation of fayalitic olivine and ferrosilite-rich pyroxene due to reaction of silica with oxidized Fe on a parent body, and (f) minor thermal metamorphism, possibly generated by impacts.