SLRS‐5 Elemental Concentrations of Thirty‐Three Uncertified Elements Deduced from SLRS‐5/SLRS‐4 Ratios

The fifth version of natural river water certified reference material, SLRS‐5 (National Research Council – Conseil National de Recherches Canada), is commonly used to control the quality of major and trace element measurements. Concentrations of silicon and thirty‐one uncertified trace elements have been reported for the certified reference material SLRS‐4, but they are not yet available for SLRS‐5. Here, SLRS‐5/SLRS‐4 ratios were deduced from SLRS‐5 and SLRS‐4 measurements by inductively coupled plasma‐atomic emission spectrometry and high‐resolution inductively coupled plasma‐mass spectrometry for certified elements and thirty‐five uncertified elements (rare earth elements, B, Bi, Br, Cs, Ga, Ge, Hf, Li, Nb, P, Pd, Rb, Rh, S, Sc, Si, Sn, Th, Ti, Tl, Y). Both reference materials were measured directly one after the other, so that calculated elemental ratios would not be notably influenced either by calibration uncertainties or by eventual long‐term instrumental drift. The computed ratios are in good agreement with those deduced from the certified values. We also report concentrations for thirty‐three uncertified elements in SLRS‐5 by combining the measured SLRS‐5/SLRS‐4 ratios and the published SLRS‐4 values. The resulting new data set provides target SLRS‐5 values, which will be useful in quality control procedures.     

Westward accretion of the Baltic Shield: implications from the 1.6 GaÅmål-Horred Belt, SW Sweden

Three new U-Pb zircon age determinations are reported from the Horred region, south-southeast of Göteborg, SW Sweden. This is a region of the Southwest Scandinavian Domain, within which a major NS trending shear zone and tectonic boundary, the Mylonite Zone, juxtaposes comparatively weakly migmatised lithologies in the west against more intensely migmatised gneisses in the east.West of the Mylonite Zone, a metavolcanic rock (the Mjösjödacite) yields an age of 1643 ± 29 Ma, whereas a cross-cutting plutonic rock (the Idala tonalite) has an age of 1584 ± 15 Ma. Together with a recent age for a volcanic rock from theÅmål region farther north (1.61 Ga, Lundqvist and Skiöld, 1992), these ages help to establish the existence of a coherent calc-alkaline igneous belt of 1.6 Ga age for which the nameÅmål-Horred Belt is proposed.East of the Mylonite Zone, a presumably metavolcanic rock (the Grimmared gneiss) yields an age of 1.61 Ga. The obtained age and the compositional similarity of rocks on each side of the Mylonite Zone indicate that more deformed and more strongly metamorphosed equivalents of the rocks in theÅmål-Horred Belt may occur also to the east of the Mylonite Zone in what is termed the Eastern Segment of the Southwest Scandinavian Domain.The new results establish theÅmål-Horred Belt as a major geological unit younger than most other crustal components in southern Sweden such as theÖstfold-Marstrand Belt ( 1.76 Ga), the Eastern Segment gneisses (> 1.66 Ga) and the three age groups of the Transscandinavian Igneous Belt ( 1.81 – 1.65 Ga; Larson and Berglund, 1992). The configuration of the crustal units in SW Sweden appears to necessitate more complex Proterozoic models than those with a persistent younging from the present east to the west.The present concept of the “Gothian orogeny” must be revised since at least two different orogenic episodes at 1.7 and 1.6 Ga can now be distinguished.     

Structure and phase transition of CaGe<Subscript>2</Subscript>O<Subscript>5</Subscript> revisited

The structure of CaGe₂O₅ between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at T_c=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e₂₃, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe₂O₅.     

Early Devensian (MIS 5d–5b) occupation at Dartford,southeast England

A deeply buried horizon containing mint‐condition flint artefacts was discovered in 2006 during archaeological investigations in advance of major roadworks near Dartford, Kent, in southeast England. The context of the artefacts and the freshness of their condition suggest this horizon represents a buried occupation surface. Optically stimulated luminescence dating places this horizon in the period Marine Isotope Stage 5d–5b, early in the British Devensian glaciation. This paper describes details of the artefacts, their context and dates, and outlines how this apparent occupation fits in with the wider pattern of Neanderthal settlement in Britain and northwest Europe in the later Pleistocene. Copyright © 2010 John Wiley & Sons, Ltd.     

A temporary glacier‐surge ice‐dammed lake,Braganzavågen,Svalbard

A prominent thrust‐moraine system formed in the inner van Mijenfjorden, Svalbard, during a surge event in a tributary fjord, creating a large temporary lake. Based on geomorphological, sedimentological, stratigraphical and chronological data, the lake began to form shortly after 648–551 cal. a BP. At its maximum, the lake covered an estimated area of 77 km² with a water volume of 1.2 km³. Lake sediment up to 80 cm thick was rapidly deposited on top of terrestrial and marine sediments. At its maximum extent, the short‐lived lake was the largest of any known Holocene lake in Svalbard. Modern river discharge would fill the lake to its highest shoreline at 23 m a.s.l. in only one season. Drainage was stepwise, as evidenced by four shorelines and abandoned drainage channels. This study has taken advantage of a unique suite of data available for such an ice‐dammed lake. The results demonstrate the power of a multidisciplinary approach for recognizing lake events in the geological record, which is essential given the low preservation potential of such sediments.     

Crustal structure of the Lofoten–Vesterålen continental margin, off Norway

By compiling wide-angle seismic velocity profiles along the 400-km-long Lofoten–Vesterålen continental margin off Norway, and integrating them with an extensive seismic reflection data set and crustal-scale two-dimensional gravity modelling, we outline the crustal margin structure. The structure is illustrated by across-margin regional transects and by contour maps of depth to Moho, thickness of the crystalline crust, and thickness of the 7+ km/s lower crustal body. The data reveal a normal thickness oceanic crust seaward of anomaly 23 and an increase in thickness towards the continent–ocean boundary associated with breakup magmatism. The southern boundary of the Lofoten–Vesterålen margin, the Bivrost Fracture Zone and its landward prolongation, appears as a major across-margin magmatic and structural crustal feature that governed the evolution of the margin. In particular, a steeply dipping and relatively narrow, 10–40-km-wide, Moho-gradient zone exists within a continent–ocean transition, which decreases in width northward along the Lofoten–Vesterålen margin. To the south, the zone continues along the Vøring margin, however it is offset 70–80 km to the northwest along the Bivrost Fracture Zone/Lineament. Here, the Moho-gradient zone corresponds to a distinct, 25-km-wide, zone of rapid landward increase in crustal thickness that defines the transition between the Lofoten platform and the Vøring Basin. The continental crust on the Lofoten–Vesterålen margin reaches a thickness of 26 km and appears to have experienced only moderate extension, contrasting with the greatly extended crust in the Vøring Basin farther south. There are also distinct differences between the Lofoten and Vesterålen margin segments as revealed by changes in structural style and crustal thickness as well as in the extent of elongate potential-field anomalies. These changes may be related to transfer zones. Gravity modelling shows that the prominent belt of shelf-edge gravity anomalies results from a shallow basement structural relief, while the elongate Lofoten Islands belt requires increased lower crustal densities along the entire area of crustal thinning beneath the islands. Furthermore, gravity modelling offers a robust diagnostic tool for the existence of the lower crustal body. From modelling results and previous studies on- and off-shore mid-Norway, we postulate that the development of a core complex in the middle to lower crust in the Lofoten Islands region, which has been exhumed along detachments during large-scale extension, brought high-grade, lower crustal rocks, possibly including accreted decompressional melts, to shallower levels.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Oxyvanite,V<Subscript>3</Subscript>O<Subscript>5</Subscript>, a new mineral species and the oxyvanite-berdesinskiite V<Subscript>2</Subscript>TiO<Subscript>5</Subscript> series from metamorphic rocks of the Slyudyanka Complex,southern Baikal region

Oxyvanite has been identified as an accessory mineral in Cr-V-bearing quartz-diopside meta- morphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. The new mineral was named after constituents of its ideal formula (oxygen and vanadium). Quartz, Cr-V-bearing tremolite and micas, calcite, clinopyroxenes of the diopside-kosmochlor-natalyite series, Cr-bearing goldmanite, eskolaite-karelianite dravite-vanadiumdravite, V-bearing titanite, ilmenite, and rutile, berdesinskiite, schreyerite, plagioclase, scapolite, barite, zircon, and unnamed U-Ti-V-Cr phases are associated minerals. Oxyvanite occurs as anhedral grains up to 0.1–0.15 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black, with black streak and resinous luster. The microhardness (VHN) is 1064–1266 kg/mm² (load 30 g), and the mean value is 1180 kg/mm². The Mohs hardness is about 7.0–7.5. The calculated density is 4.66(2) g/cm³. The color of oxyvanite is pale cream in reflected light, without internal reflections. The measured reflectance in air is as follows (λ, nm-R, %): 440-17.8; 460-18; 480-18.2; 520-18.6; 520-18.6; 540-18.8; 560-18.9; 580-19; 600-19.1; 620-19.2; 640-19.3; 660-19.4; 680-19.5; 700-19.7. Oxyvanite is monoclinic, space group C2/c; the unit-cell dimensions are a = 10.03(2), b = 5.050(1), c = 7.000(1) Å, β = 111.14(1)°, V = 330.76(5)ų, Z = 4. The strongest reflections in the X-ray powder pattern [d, Å, (I in 5-number scale)(hkl)] are 3.28 (5) (20\(\bar 2\)); 2.88 (5) (11\(\bar 2\)); 2.65, (5) (310); 2.44 (5) (112); 1.717 (5) (42\(\bar 2\)); 1.633 (5) (31\(\bar 4\)); 1.446 (4) (33\(\bar 2\)); 1.379 (5) (422). The chemical composition (electron microprobe, average of six point analyses, wt %): 14.04 TiO₂, 73.13 V₂O₃ (53.97 V₂O_3calc, 21.25 VO_2calc), 10.76 Cr₂O₃, 0.04 Fe₂O₃, 0.01 Al₂O₃, 0.02 MgO, total is 100.03. The empirical formula is (V _1.70 ³⁺ Cr_0.30)_2.0(V _0.59 ⁴⁺ Ti_0.41)_1.0O₅. Oxyvanite is the end member of the oxyvanite-berdesinskiite series with homovalent isomorphic substitution of V⁴⁺ for Ti. The type material has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Calibration of the garnet–biotite–Al2SiO5–quartz geobarometer for metapelites

A garnet–biotite–Al₂SiO₅–quartz (GBAQ) geobarometer was empirically calibrated using more than 700 natural metapelites with a broad compositional range of garnet and biotite under P–T conditions of 450–950°C and 1–17 kbar. In the calibration, activity models of garnet and biotite identical to those in the garnet–biotite (GB) geothermometer of Holdaway [American Mineralogist 2000, 85: 881–892] were used. Therefore, the GBAQ geobarometer and the GB geothermometer can be simultaneously applied to iteratively estimate metamorphic P–T conditions. Successful applications of the GBAQ geobarometer to natural metapelites certify its validity. Most importantly, when plagioclase is absent or CaO components in garnet and/or plagioclase are deficient, this geobarometer may prove useful for estimating metamorphic pressures. The random error of the present GBAQ geobarometer is inferred to be around ±1.8 kbar. An electronic spreadsheet is available as Table S4 to apply the GBAQ geobarometer in combination with the GB geothermometer.     

Rare earth elements in vivianite from Lake Åstrum

The rare carth elements are determined in vivianite concretions and surrounding clay sediments. Approximately 3/4 of the rare earth elements in the clay is present in adsorbed state. The concentration of REE in the pore water is calculated from the composition of the vivianite, assuming a diffusion model for the formation of the concretions and lower solubility of the rare earth elements above the concretions than in the pore water at some distance from the concretions. The concentrations thus calculated are similar to published values for ocean water.     

Jonassonite (AuBi<Subscript>5</Subscript>S<Subscript>4</Subscript>) from the Dakripen gold deposit in Vietnam

For the first time in ore deposits of Vietnam, a mineral phase containing Au, Bi, and S as major elements was found in the gold ore of the Dakripen deposit. Pb is also present as a minor isomorphic impurity. Rare irregular or ellipsoid grains of that mineral up to 35 μm in size were identified in polished sections together with pyrite; galena; sphalerite; bismuthinite; ikunolite; native bismuth; and, occasionally, gold. All these species are related to the third stage of the ore formation. In reflected light, the mineral is bluish white, the reflectance is comparable with ikunolite and slightly higher than that of bismuthinite, and weak pleochroism and visible anisotropy are established. The mineral is opaque and brittle without internal reflections. According to 18 microprobe analyses, its average chemical composition and quantitative variations for the major elements are as follows (wt %): 14.02 (13.11–14.58) Au, 76.37 (74.93–76.91) Bi, 0.49 (0.10–1.00) Pb, 9.80 (8.87–10.07) S, and 100.68 in total. The empirical formula calculated for the average element contents—Au_0.96(Bi_4.91Pb_0.03)_4.94S_4.10—is similar to the idealized formula of jonassonite from the Nagybörzsöny deposit (Hungary)—Au(Bi,Pb)₅S₄—approved by the Commission on New Minerals and Mineral Names of the International Mineralogical Association. The typical mineral assemblage, optical properties, and chemical composition of this mineral allow us to regard it as a low-Pb variety of jonassonite. It may be assumed that the real formula of jonassonite without sporadic impurities of Pb and other elements must be AuBi₅S₄, as was stated before in the first communication of the Commission on New Minerals and Mineral Names of the International Mineralogical Association and is typical of minerals from Kazakhstan, Russia, Japan, Germany, the Czech Republic, the United States, and Australia.     

Holocene environmental history of the Ångermanälven Estuary,northern Baltic Sea

The Baltic Sea has experienced a complex geological history, with notable swings in salinity driven by changes to its connection with the Atlantic and glacio‐isostatic rebound. Sediments obtained during International Ocean Drilling Program Expedition 347 allow the study of the effects of these changes on the ecology of the Baltic in high resolution through the Holocene in areas where continuous records had not always been available. Sites M0061 and M0062, drilled in the Ångermanälven Estuary (northern Baltic Sea), contain records of Holocene‐aged sediments and microfossils. Here we present detailed records of palaeoecological and palaeoenvironmental changes to the Ångermanälven Estuary inferred from diatom, palynomorph and organic‐geochemical data. Based on diatom assemblages, the record is divided into four zones that comprise the Ancylus Lake, Littorina Sea, Post‐Littorina Sea and Recent Baltic Sea stages. The Ancylus Lake phase is initially characterized as oligotrophic, with the majority of primary productivity in the upper water column. This transition to a eutrophic state continues into the Initial Littorina Sea stage. The Initial Littorina Sea stage contains the most marine phase recorded here, as well as low surface water temperatures. These conditions end before the Littorina Sea stage, which is marked by a return to oligotrophic conditions and warmer waters of the Holocene Thermal Maximum. Glacio‐isostatic rebound leads to a shallowing of the water column, allowing for increased benthic primary productivity and stratification of the water column. The Medieval Climate Anomaly is also identified within Post‐Littorina Sea sediments. Modern Baltic sediments and evidence of human‐induced eutrophication are seen. Human influence upon the Baltic Sea begins c. 1700 cal. a BP and becomes more intense c. 215 cal. a BP.     

Photocatalytic degradation of imidacloprid in aqueous suspension of TiO<Subscript>2</Subscript> supported on H-ZSM-5

The composite of TiO₂ and zeolite H-ZSM-5 has great photocatalytic ability for organic contaminants over a very large specific surface area and highlighted adsorption capacity. To describe abiotic degradation of imidacloprid, the photoinduced degradation of the pesticide imidacloprid in aqueous solutions, in the presence of TiO₂ supported on H-ZSM-5 as photocatalyst, was performed. The study focused on the comparison of the imidacloprid degradation between photolysis and photocatalysis. The experimental results showed that the degradation of imidacloprid was more rapid in the condition of photocatalytic than that of photolysis or TiO₂-only. The identification of possible intermediate products during the degradation was investigated by the high-performance liquid chromatography coupled with electrospray time-of-flight mass spectrometry (HPLC/TOF-MS). The main photocatalytic products were identified as chloronictinic acid, 1-[(6-chloro-3-pyridinyl) methyl]-2-imidazolidinone and 1-[(6-chloro-3-pyridinyl) methyl]-N-nitroso-2-imidazolidimine.     

Saalian to Weichselian stratigraphy and sedimentation along the Lågjæren – Høgjæren escarpment,southwest Norway

Quaternary sediments along a profile crossing the southern part of the Jæren escarpment, southwestern Norway, have been investigated with regard to their glacial history and sea-level variations. Deposits from at least three glaciations and two ice-free periods between Oxygen Isotope Stage 6 and the Late Weichselian have been identified. Subglacial till directly overlain by a glaciomarine regressional succession indicates a deglaciation, and amino acid ratios in Elphidium excavatum between 0.083 and 0.118 date this event to Oxygen Isotope Stage 6. Sea-level dropped from 130 to below 110 m a.s.l. Subsequently, a short-lived ice advance deposited a marginal moraine and a sandur locally on the escarpment. Stratigraphical position and luminescence dates around 148 ka BP suggest deposition during the final stage 6 deglaciation. A Late Weichselian till covers most of the surface of Jæren. In addition to a well documented westerly ice flow, glaciotectonic indications of ice flow towards the north have been found. Ice flow directions and a hiatus between Oxygen Isotope Stage 6 and the Weichselian indicate enhanced erosion along the escarpment and the influence of a Norwegian Channel ice-stream. Copyright © 1999 John Wiley & Sons, Ltd.     

Slow cooling versus episodic fluid injections: Deciphering the Caledonian orogeny in Vestvågøy,Lofoten islands,Norway

The determination of the thermal (temperature–time) histories of high‐P metamorphic terranes has been commonly based on the concepts of slow cooling and closure temperatures. In this paper, we find that this approach cannot reconcile a geochronological data set obtained from the amphibolite‐facies allochthonous Leknes Group of the Lofoten islands, Norway, which reveals an extremely complex thermal history. Using detailed results from several different geochronometers such as ⁴⁰Ar/³⁹Ar, Rb–Sr and U–Pb, we show that a model invoking multiple, short‐lived thermal pulses related to hot‐fluid infiltration channelized by shear zones can reconcile this complicated data set. This model suggests that hot fluids infiltrated throughout basement shear zones and affected the overlying cold allochthon, partially resetting U/Pb rutile and titanite ages, crystallizing new zircon and produced identical ⁴⁰Ar/³⁹Ar and Rb/Sr ages in muscovite, biotite and amphibole in various rocks throughout the region. This paper shows the enormous potential of coupling laser Ar‐spot data with thermal modelling to identify and constrain the duration of short‐lived events. An optimal P–T–t history has been derived by modelling the age data from a previously dated large muscovite crystal (Hames & Andresen, 1996, Geology, 24 :1005) and using Zr‐in‐rutile thermometry which is consistent with all geochronological data and geological constraints from the basement zones and allochthon cover. This tectonothermal model history suggests that there have been three episodic hot‐fluid and ⁴⁰Ar‐free infiltration events, resulting in the total resetting of Ar ages during the Scandian (425 Ma) for 1 Ma at 650°C and two reheating events at 415 Ma for 400 ka at 650°C and at 365 Ma for 50 ka at 600°C, which are modelled as thermal spikes above an ambient temperature of 300°C. Independent confirmation of these parameters was provided by Pb‐diffusion modelling in rutile and titanite. The model suggests that the amphibolite facies rocks of the Leknes Group probably remained cold before being exhumed for at least 60 Ma (425–365 Ma) and successfully explains the presence of different minerals that crystallized or were totally/partially reset in the allochthon and in the basement. The migration of hot fluids for short periods of times within conduits extending through the basement and allochthon rock units is likely associated with episodic seismic activity during the Caledonian orogeny.     

The basic parameters of acceleration spectra for M > 5 earthquakes in the Baikal Rift Zone

We consider the acceleration spectra of S waves from M = 5-6.5 earthquakes that occurred in three regions of the Baikal Rift Zone. The main characteristics of the shape and level of the spectra are given, and the difference between the spectra in the relative positions of the focus and seismic station is shown. Average acceleration spectra have been obtained for all three regions with regard to shape and the magnitude of the earthquakes. The spectra have been transformed so that they correspond to the accelerations of M = 6.5 and M = 7.5 earthquakes. The conclusion is made that the spectra not necessarily retain their shape even with the same movements in the focus.