Volatile-induced transport of HFSE, REE, Th and U in arc magmas: evidence from zirconolite-bearing vesicles in potassic lavas of Lewotolo volcano (Indonesia)

Potassium-rich calc-alkaline lavas of Lewotolo volcano, situated in the East Sunda Arc, Indonesia, contain the rare mineral zirconolite (CaZrTi₂O₇). Samples in which tiny grains of this mineral (3–25 μm in size) were found span the entire range of lava compositions (47–62 wt% SiO₂). To the best of our knowledge, this is the first record of primary zirconolite in juvenile arc volcanics. The mineral forms part of a vesicle-filling assemblage consisting of a network of quenched feldspar crystals and an SiO₂ phase, probably cristobalite. High contents of Th, U and REE (up to 9.3, 4.3 and 15.6 wt% oxide respectively) and very high Fe contents (up to 13.5 wt% Fe₂O₃) distinguish these zirconolites from those of other rock types. The extraction of volatile-rich phases with changing compositions in successive stages is considered to be responsible for the zirconolite formation. We hypothesise that a fluid capable of transporting HFSE, REE, Th and U was extracted from the magma and (partly) crystallised within voids which had formed earlier upon saturation of an aqueous fluid. Assuming that zirconolite compositions largely reflect trace metal contents of the coexisting fluid phase, significant amounts of `immobile' elements must have been transported on a macroscopic scale. Our findings thus point to a late-stage transfer of HFSE, REE, Th and U between different domains in a cooling magma body. Such a volatile-induced redistribution of trace elements at shallow levels of high-K volcanic systems may be significant for conventional geochemical modelling of magma evolution and for Th–U disequilibrium studies. Received: 3 November 1999 / Accepted: 29 February 2000     

The Ordovician chondrite from Brunflo, central Sweden: III. Geochemistry of terrestrial alteration

The fossil H chondrite Brunflo, found in a slab of Ordovician limestone from central Sweden, is pervasively altered to an assemblage dominated by calcite and barite. The meteorite is surrounded by a 15–20 cm wide zone of lighter colors than the unaffected limestone due to dissolution of hematite. Here we present detailed geochemical analyses of two meteorite samples, 14 limestone samples at distances from 0 to 29 cm along two profiles from the meteorite, and a reference sample of Brunflo limestone. Element concentrations in Brunflo and surrounding bleached limestone have been strongly disturbed during two stages of alteration (early oxygenated and deep burial). In the meteorite, the Ni/Co ratio has changed from an initial value of 20 to 0.8 and redox sensitive elements like V, As, Mo, Re and U are strongly enriched. The sulfur isotope composition of barite from Brunflo (δ³⁴S=+35‰) indicates initial loss of meteoritic sulfide, followed by later accumulation of sea water sulfate as barite. During deep burial under more reducing conditions, reduction processes supported by an externally derived reductant possibly derived from alum shale underlying the limestone, were largely responsible for the observed redox phenomena. In spite of massive redistribution of many elements, concentrations of Pt, Ir and Au remain at chondritic levels. The geochemistry and mineralogy of alteration determined for Brunflo are similar to those in “reduction spots” in red beds, where accumulation of a similar suite of elements (except Mo, Re) occurred as a result of isolated reduction activity.     

Identifying causes of ground-penetrating radar reflections using time-domain reflectometry and sedimentological analyses

Ground-penetrating radar (GPR) is a geophysical technique widely used to study the shallow subsurface and identify various sediment features that reflect electromagnetic waves. However, little is known about the exact cause of GPR reflections because few studies have coupled wave theory to petrophysical data. In this study, a 100- and 200-MHz GPR survey was conducted on aeolian deposits in a quarry. Time-domain reflectometry (TDR) was used to obtain detailed information on the product of relative permittivity (ɛ_r) and relative magnetic permeability (μ_r), which mainly controls the GPR contrast parameter in the subsurface. Combining TDR data and lacquer peels from the quarry wall allowed the identification of various relationships between sediment characteristics and ɛ_rμ_r. Synthetic radar traces, constructed using the TDR logs and sedimentological data from the lacquer peels, were compared with the actual GPR sections. Numerous peaks in ɛ_rμ_r, which are superimposed on a baseline value of 4 for dry sand, are caused by potential GPR reflectors. These increases in ɛ_rμ_r coincide with the presence of either organic material, having a higher water content and relative permittivity than the surrounding sediment, or iron oxide bands, enhancing relative magnetic permeability and causing water to stagnate on top of them. Sedimentary structures, as reflected in textural change, only result in possible GPR reflections when the volumetric water content exceeds 0·055. The synthetic radar traces provide an improved insight into the behaviour of radar waves and show that GPR results may be ambiguous because of multiples and interference.     

In situ bioremediation of 1,2-dichloroethane under anaerobic conditions

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam–Botlek area in The Netherlands has lead to deep-seated pollution of the underlying aquifer. The principal pollutant is 1,2-dichloroethane (1,2-DCA). As a temporary measure, the contamination is being contained using a pump and treat system. In the long term, in-situ bioremediation has been proposed using a biologically active zone where pollutants would be dechlorinated by microorganisms that simultaneously degrade other carbon sources. In order to investigate the suitability of this new technology, a programme of laboratory tests was carried out. The laboratory programme involved a series of anaerobic soil column tests, where the selection and delivery of different carbon substrates that stimulated 1,2-DCA dechlorination were investigated. The soil columns were prepared using soil and groundwater samples from boreholes. Groundwater was flushed through the columns under anaerobic conditions. A comparison was made between the transformation of 1,2-DCA without a carbon substrate and in the presence of sugars (molasses) and alcohol (methanol) respectively. In addition, different modes of delivery were investigated. In the case of molasses, the material was injected into the column as a plug to simulate grout injection in the field, whereas methanol was delivered as a constant flow dissolved in the influent. Both carbon substrates resulted in the biotransformation of 1,2-DCA. However, fermentation of molasses produced secondary effects that led to a drop in pH and an excessive production of carbon dioxide, which temporarily blocked the flow of groundwater.     

Recent Climate Warming: Surface Air Temperature Series and Geothermal Evidence

Long-term (1961 – 1996) meteorological air temperature series together with the reconstructed ground surface temperature histories, obtained by inverting borehole temperature-depth profiles, were used to project regional patterns of the recent (climate) warming rate on the territory of the Czech Republic. The characteristic magnitude of the warming rate of 0.02 –0.03 K/yr was confirmed by the results of several years of monitoring the temperature in two experimental boreholes. The monitoring of shallow temperatures at depths of about 30 –40 m, i.e. below the reach of the seasonal surface temperature variations, can serve as an alternative tool of direct quantitative assessment of the present warming rate. The data also seem to sustain a potential man-made component contributing to the more pronounced recent warming rate observed in the areas of large agglomeration.     

Contribution of Local Seismic Networks To The Regional Velocity Model of The Bohemian Massif

The routine location of regional seismic events using data from the Czech National Seismological Network (CNSN) is based on Pn, Pg, Sn, Sg phases. A simple velocity model derived from Kárník's (1953) interpretation of an earthquake in Northern Hungary in 1951 has hitherto been used. At present, numerous local seismic networks record and locate local events, which are occasionally recorded at regional distances as well. Due to the relatively small dimensions of local networks, hypocenters (and origin times) determined by a local network might be considered as nearly exact from the point of view of regional-scale CNSN. The comparison of common locations performed by CNSN and by a local network enables us to estimate the accuracy of CNSN locations, as well as to optimize a simple velocity model. The joint interpretation of the CNSN bulletin and the catalogues of four local seismic networks WEBNET, OSTRAVA, KLADNO and LUBIN produced a new ID velocity model. The most frequent epicentral error in this model is less than 5 km, and most foci lie up to 15 km from the true position. The performed analysis indicates bimodal distribution of Sn residuals.     

The evolution of the Dutch and Belgian coasts and the role of sand supply from the North Sea

During the Holocene, the Dutch and Belgian coasts evolved, controlled by post-glacial eustatic sea-level rise, spatially varying vertical subsurface motions (glacio-isostatic crustal rebound, compaction, tectonics) and spatially varying sediment supply (mainly marine sand). The marine sand supply changed as the tidal dynamics and the wave climate changed due to the changing geometry and depth of the North Sea during the Holocene transgression. These changes influenced the coastal evolution. This study compares the results of separate numerical model calculations of the large-scale Holocene tide- and wave-induced sand transport in the southern North Sea with existing geological data of the Dutch and Belgian large-scale coastal evolution, resulting in a qualitatively good correlation. The large-scale coastal evolution is interpreted in terms of the oceanographical forcing, and an integrated conceptual model of the Holocene evolution of the Dutch and Belgian coasts is proposed. The large-scale wave-driven bed-load transport was an order of magnitude smaller than the tidal transports. The modelled tidal transport direction changed from onshore before 6 ka BP to along shore at present for the Zeeland and Holland coasts; the influence that waves may have had on the tidal transport by suspending sand gradually decreased. This change in direction caused the modelled tidal sand supply to the coast to decrease for the Belgian, Zeeland and Holland coasts. While the offshore area of the Holland coast remained a zone of (small) deposition due to decreasing northward sand transports, the offshore area of the Zeeland coast became increasingly erosional after 6 ka BP due to the encroaching divergence of the tidal transports. Due to uncertainty in the magnitude of the modelled sand transports, but robustness in the transport patterns, the focus is on the qualitative rather than the quantitative model results. When compared with the trend of closure, expansion and later erosion and reopening of the coast, the above decrease in sand supply must have been slow enough compared with the decrease in sea-level rise to cause a temporary sand surplus which decayed to a slight deficit as the decrease in supply and the rise in sea level continued. The Wadden Sea coast exchanged little or no sand with the adjacent deeper North Sea throughout the Holocene.     

Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

Nonlinear and 3D effects in leaky infragravity waves

In this paper, infragravity (IG) waves, forced by normally and obliquely incident wave groups, are studied using the quasi-3D (Q3D) nearshore circulation model SHORECIRC [Van Dongeren, A.R., I.A. Svendsen, 1997b. Quasi 3-D modeling of nearshore hydrodynamics. Research report CACR-97-04. Center for Applied Coastal Research, University of Delaware, Newark, 243 pp.], which includes the Q3D effects. The governing equations that form the basis of the model, as well as the numerical model and the boundary conditions, are described. The model is applied to the case of leaky IG waves. It is shown that the Q3D terms have a significant effect on the cross-shore variation of the surface elevation envelope, especially around the breakpoint and in the inner surf zone. The effect of wave groupiness on the temporal and spatial variation of all Q3D terms is shown after which their contribution to the momentum equations is analyzed. This reveals that only those Q3D coefficients, which appear in combination with the largest horizontal velocity shears make a significant contribution to the momentum equations. As a result of the calculation of the Q3D coefficients, the IG wave velocity profiles can be determined. This shows that in the surf zone, the velocity profiles exhibit a large curvature and time variation in the cross-shore direction, and a small — but essential — depth variation in the longshore direction.