Determination of Free Cd,Cu and Zn Concentrations in Lake Waters by In Situ Diffusion Followed by Column Equilibration Ion-exchange

Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter—DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19–2.9 nM; [Cu] 36–190 nM; [Zn] 7–2,800 nM. The proportion of total dissolved metal present as free Cd²⁺ and Zn²⁺ was relatively constant for the 14 selected lakes, despite the wide pH (4.5–8) and DOM (3–23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.     

A rapid, partial leach and organic separation for the sensitive determination of Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn in surface geologic materials by flame atomic absorption

A solution of dilute hydrochloric acid, ascorbic acid, and potassium iodide has been found to dissolve weakly bound metals in soils, stream sediments, and oxidized rocks. Silver, Bi, Cd, Cu, Mo, Pb, Sb, and Zn are selectively extracted from this solution by a mixture of Aliquat 336 (tricaprylyl methyl ammonium chloride) and MIBK (methyl isobutyl ketone). Because potentially interfering major and minor elements do not extract, the organic separation allows interference-free determinations of Ag and Cd to the 0.05 ppm level, Mo, Cu, and Zn to 0.5 ppm, and Bi, Pb, and Sb to 1 ppm in the sample using flame atomic absorption spectroscopy. The analytical absorbance values of the organic solution used in the proposed method are generally enhanced more than threefold as compared to aqueous solutions, due to more efficient atomization and burning characteristics. The leaching and extraction procedures are extremely rapid; as many as 100 samples may be analyzed per day, yielding 800 determinations, and the technique is adaptable to field use.The proposed method was compared to total digestion methods for geochemical reference samples as well as soils and stream sediments from mineralized and unmineralized areas. The partial leach showed better anomaly contrasts than did total digestions. Because the proposed method is very rapid and is sensitive to pathfinder elements for several types of ore deposits, it should be useful for reconnaissance surveys for concealed deposits.     

Frontiers in large igneous province research

Earth history is punctuated by events during which large volumes of mafic magmas were generated and emplaced by processes distinct from “normal” seafloor spreading and subduction-related magmatism. Large Igneous Provinces (LIPs) of Mesozoic and Cenozoic age are the best preserved, and comprise continental flood basalts, volcanic rifted margins, oceanic plateaus, ocean basin flood basalts, submarine ridges, ocean islands and seamount chains. Paleozoic and Proterozoic LIPs are typically more deeply eroded and are recognized by their exposed plumbing system of giant dyke swarms, sill provinces and layered intrusions. The most promising Archean LIP candidates (apart from the Fortescue and Ventersdorp platformal flood basalts) are those greenstone belts containing tholeiites with minor komatiites. Some LIPs have a substantial component of felsic rocks. Many LIPs can be linked to regional-scale uplift, continental rifting and breakup, climatic shifts that may result in extinction events, and Ni–Cu–PGE (platinum group element) ore deposits.

Some current frontiers in LIP research include:

(1) Testing various mantle plume and alternative hypotheses for the origin for LIPs.

(2) Characterizing individual LIPs in terms of (a) original volume and areal extent of their combined extrusive and intrusive components, (b) melt production rates, (c) plumbing system geometry, (d) nature of the mantle source region, and (e) links with ore deposits.

(3) Determining the distribution of LIPs in time (from Archean to Present) and in space (after continental reconstruction). This will allow assessment of proposed links between LIPs and supercontinent breakup, juvenile crust production, climatic excursions, and mass extinctions. It will also allow an evaluation of periodicity in the LIP record, the identification of clusters of LIPs, and postulated links with the reversal frequency of the Earth's magnetic field.

(4) Comparing the characteristics, origin and distribution of LIPs on Earth with planets lacking plate tectonics, such as Venus and Mars. Interplanetary comparison may also provide a better understanding of convective processes in the mantles of the inner planets.

In order to achieve rapid progress in these frontier areas, a global campaign is proposed, which would focus on high-precision geochronology, integrated with paleomagnetism and geochemistry. Most fundamentally, such a campaign could help hasten the determination of continental configurations in the Precambrian back to 2.5 Ga or greater. Such reconstructions are vital for the proper assessment of the LIP record, as well as providing first-order information related to all geodynamic processes.     

Composition-volume changes during hydrothermal alteration of andesite at Buttercup Hill, Noranda District, Quebec

Hydrothermally altered andesites in the upper member of the Amulet formation at Buttercup Hill, Noranda, Quebec represent part of the aquifer and cap of a self-sealing geothermal system that focussed the discharge of hydrothermal fluids during the formation of massive Cu-Zn sulfide deposits. Five alteration facies are recognized

1. 1) pervasive greenschist faciés regional metamorphism (least-altered andesite)

2. 2) epidotization-silicification

3. 3) albitization-silicification

4. 4) chloritization

5. 5) sericitization-silicification. Alteration is localized on permeable zones such as amygdules, fractures, flow tops, discordant breccia dikes, and conformable breccia horizons.

Epidotized-silicified andesite is enriched in Ca-Sr-Eu and depleted in Mg and first transition series metals (FTSM) relative to least-altered andesite. Albitized-silicified andesite is significantly enriched in Na and depleted in most FTSM relative to least-altered andesite. The abundances and inter-element ratios of the rare-earth elements (REE) and most high field-strength elements (HFS: Y, Zr, Th, U, Hf, Ta) are similar in least-altered, epidotized-silicified and albitized-silicified andesites. The most silicified andesites are strongly enriched in Na-Si, strongly depleted in Mg and divalent FTSM and slightly but systematically depleted in REE and most HFS elements. Serialized andesites were previously silicified; they are very strongly enriched in K-Rb-Cs-Ba, very strongly depleted in Na-Ca-Sr-Eu and slightly depleted in light REE relative to silicified andesite. Chloritized andesitic rocks exhibit heavy REE and HFS element ratios similar to those of leastaltered andesite, but are relatively strongly enriched in Mg and divalent FTSM, strongly depleted in Si and large ion lithophile (LIL) elements and slightly depleted in light REE.

The coupled behavior of the heavy REE and most HFS elements during epidotization, albitization, silicification, chloritization and serialization suggests that they were inert during hydrothermal modification of the andesite. Mass balance calculations suggest that volume was conserved during epidotization-silicification and albitization-silicification, but that intense silicification was accompanied by volume increases up to 30 percent.     

Cultural sediment analyses and transitions in early fishing activity at Langenesværet,Vesterålen,Northern Norway

The development of specialized and commercial fishing activity in the island archipelago of Lofoten and Vesterålen in northern Norway is a critical foundation from which to understand the subsequent spread of commercial fishing across the north Atlantic region during the medieval and early modern period. One little understood aspect of this development is the relationship between medieval commercial fishing stations (fiskevaer) and earlier fishing activity. In this article, cultural sediment deposits at Langenesværet, Vesterålen, Northern Norway provide an opportunity to examine this relationship and its implications for current historical models of fishing development in northern Norway and the north Atlantic region. Conventional and AMS radiocarbon dating techniques are used to establish a chronology for the deposits, while activities associated with the sediments are characterized using thin‐section micromorphology supported by proton induced X‐ray emission spectrometry (PIXE). The results suggest that the site commenced formation as early as ca. 3000 B.C. and that the site was first used for specialized fishing activity from the early centuries A.D. The medieval commercial fiskevaer settlement at Langenesværet was introduced to an area that had a longstanding tradition of specialised fishing activity. © 2000 John Wiley & Sons, Inc.     

Preliminary study on the preservation of giant clam (Tridacnidae) shells from the Balobok Rockshelter archaeological site,south Philippines

Tridacnidae shells, a valuable archive of past environments, are common in the Balobok Rockshelter archaeological site on Sanga‐Sanga Island in the south Philippines. This site was occupied during the mid‐Holocene (ca. 5000–8800 ¹⁴C yr B.P.), a period of Neolithic cultural expansion in the Philippines. This paper focuses on the preservation of two shell specimens, Hippopus hippopus and Tridacna maxima, unearthed from two mid‐Holocene layers within the rockshelter. The shells' mineralogy and microstructure (prismatic and crossed‐lamellar) were studied using micro‐Fourier transform infrared spectroscopy and scanning electron microscopy to determine if the samples were suitable as paleoenvironmental records. Both shells are still aragonitic but aragonite crystals of both microstructure types are partly dissolved. This dissolution, characteristic of meteoric water alteration, precludes their utility in paleoenvironmental geochemical studies. Nevertheless, these shells are abundant in archaeological sites in the region and may be better preserved in other depositional contexts; more studies on Philippine Tridacnidae shell diagenesis are needed. © 2011 Wiley Periodicals, Inc.     

A Fissure-Controlled Acidic Volcanic Centre (Ordovician) at Yr Arddu,North Wales

The Yr Arddu Tuffs (Ordovician) are a sequence of predominantly welded acid ash-flow tuffs in the outlier centred on Yr Arddu (North Wales). The tuffs accumulated above a NNE-trending fracture, the Yr Arddu Fracture, which had previously influenced sedimentation. The heterogeneity of the tuffs and their restricted development suggest that they represent proximal accumulations from small or suppressed (boiling-over) eruption columns. The eruptions and emplacement developed, at least in the initial stages, in a submarine environment. Lithological, geochemical and palaeontological evidence indicates that the tuffs represent the earliest eruptive phase of the Lower Rhyolitic Tuff Formation. They were later intruded by comagmatic rhyolite domes, whose alignment reflects the continued influence of the early fracture.