New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε_Nd and ε_Hf both decrease with water depth. Similarly, ε_Nd and ε_Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.     

Anomalies in rare earth distributions in seawater: Gd and Tb

We have measured profiles of the rare earth elements (REE) in Atlantic and Pacific Ocean waters. The data, normalized versus shales, exhibit a pronounced anomaly in Gd relative to its neighbors Eu and Tb in the REE series such that the Gd concentrations are high by 30–50%. Closer inspection reveals that the anomaly is made up of both elevated Gd and depressed Tb concentrations, likely associated with solution chemistry shifts in the transition from an exactly half filled 4f electron shell. Anomalies in Gd and Tb solution complexation are also indicated by the Turner-Whitfield-Dickson speciation model. The overall trend of heavy REE(III) enrichment in seawater and the $\text{Gd}\text{Tb}$ anomaly described here tend to support scavenging as an important removal mechanism for the REE from seawater.     

Geology of the Ranger Uranium Mine, Northern Territory, Australia: structural constraints on the timing of uranium emplacement

The geology of the No 1 and 3 pits at the Ranger Mine in the Pine Creek Inlier (PCI) of Australia is dominated by Palaeoproterozoic volcanic, carbonate and sedimentary sequences that unconformably overlie Archaean granitic gneiss of the Nanambu Complex (2470±50 Ma). These sequences are folded, faulted and sheared, and crosscut by east-trending granite (sensu stricto) dykes and pegmatite veins, and gently dipping N–NE trending mafic dykes of the Oenpelli Dolerite (1690 Ma). Regional metamorphism is to greenschist facies and contact metamorphism is to hornblende-hornfels facies.The rocks of the Ranger Mine have been subjected to at least two phases of ductile–brittle deformation (D2–D3) and one phase of brittle deformation (D4). These events were preceded by regional diastathermal or extension-related metamorphism (D1) and the development of an ubiquitous bedding-parallel cleavage (S1).D2 resulted in the development of NNE–NNW trending mesoscopic folds (F2) and a network of thrusts and dextral reverse shears. The modelled palaeo-stress directions for the emplacement of pegmatite veins suggests that they formed early in D2. D3 resulted in the development of WNW–NW trending mesoscopic folds (F3), a weakly defined axial planar cleavage (S3) and sinistral reactivation of D2 shears. D2–D3 are correlated with deformation during the Maud Creek Event of the Top End Orogeny (1870–1780 Ma), while the emplacement of granite dykes and pegmatite veins is correlated with emplacement of regional granites at 1870–1860 Ma.D4 is associated with brittle deformation and resulted in the development of normal faults and fault breccias during a period of east–west extension. This event is correlated with regional east–west extension during deposition of Palaeo- to Mesoproterozoic platform sequences.The sequence of tectonic events established in this study indicates that uranium-bearing ore shoots in the Ranger No 1 and 3 pits formed during extension in D4, and after emplacement of the Oenpelli Dolerite at 1690 Ma. However, the currently accepted 1737±20 U–Pb Ma age places the mineralising event at time of regional post-orogenic erosion, after the Top End Orogeny and before emplacement of the Oenpelli Dolerite and extension in D4. The U–Pb age is not consistent with Sm–Nd ages for primary uranium mineralisation at Nabarlek and Jabiluka at 1650 Ma [Econ. Geol. 84 (1989) 64] and does not concur with currently accepted regional tectonic data of Johnston [Johnston, J.D., 1984. Structural evolution of the Pine Creek Inlier and mineralisation therein, Northern Territory, Australia. Unpublished PhD Thesis, Monash University, Australia], Needham et al. [Precambrian Res. 40/41 (1988) 543] and others. Consequently, the absolute age of uranium mineralisation at the Ranger Mine is open.     

An integrated approach for assessing the relative significance of human pressures and environmental forcing on the status of Large Marine Ecosystems

An ecosystem approach to the management of the marine environment has received considerable attention over recent years. However, there are few examples which demonstrate its practical implementation. Much of this relates to the history of existing marine monitoring and assessment programmes which (for many countries) are sectoral, making it difficult to integrate monitoring data and knowledge across programmes at the operational level.To address this, a scientific expert group, under the auspices of the International Council for the Exploration of the Sea (ICES), prepared a plan for how ICES could contribute to the development of an Integrated Ecosystem Assessment (IEA) for the North Sea by undertaking a pilot study utilising marine monitoring data. This paper presents the main findings arising from the expert group and in particular it sets out one possible integrated approach for assessing the relative significance of environmental forcing and fishing pressure on the ecological status of the North Sea, it then compares the findings with assessments made of other Large Marine Ecosystems (LMEs).We define the North Sea ecosystem on the basis of 114 state and pressure variables resolved as annual averages between 1983 and 2003 and at the spatial scale of ICES rectangles. The paper presents results of integrated time-series and spatial analysis which identifies and explains significant spatial and temporal gradients in the data. For example, a significant shift in the status of the North Sea ecosystem (based upon 114 state-pressure variables) is identified to have occurred around 1993. This corresponds to previously documented shifts in the environmental conditions (particularly sea surface temperature) and changes in the distribution of key species of plankton (Calanus sp.), both reported to have occurred in 1989. The difference in specific timing between reported regime shifts for the North Sea may be explained, in part, by time-lag dependencies in the trophic structure of the ecosystem with shifts in higher trophic levels occurring later than 1989.By examining the connection (or relatedness) between ecosystem components (e.g. environment, plankton, fish, fishery and seabirds) for the identified regime states (1983–1993; 1993–2003) we conclude that both the North Sea pelagic and benthic parts of the ecosystem were predominantly top-down (fishery) controlled between 1983 and 1993, whereas between 1993 and 2003 the pelagic stocks shifted to a state responding mainly to bottom-up (environment) influences. However, for the demersal fish stocks between 1993 and 2003 top-down (fishery) pressure dominated even though over this period significant reductions in fishing pressure occurred. The present analysis, therefore, provides further evidence in support of the need for precautionary management measures taken in relation to setting fishery quotas.     

CO2 in the Weddell Gyre and Antarctic Circumpolar Current: austral autumn and early winter

Quasi-continuous fugacity of CO₂ (fCO₂) data were collected in the eastern Weddell Gyre and southern Antarctic Circumpolar Current (ACC) of the Southern Ocean during austral autumn 1996. Full depth Total CO₂ (TCO₂) sections are presented for austral autumn and winter (1992) cruises. Pronounced fCO₂ gradients were observed at the Southern Ocean fronts. In the Weddell Gyre, fCO₂ regimes appeared to coincide with surface and subsurface hydrographic regimes. The southern ACC was supersaturated with respect to CO₂, as was part of the northern Weddell Gyre. The southern Weddell Gyre was markedly undersaturated. The great potential of autumn cooling for generating undersaturation and CO₂ uptake from the atmosphere was demonstrated. In the northeastern Weddell Gyre, upwelling of CO₂- and salt-rich deep water was shown to play a role as the horizontal fCO₂ distribution closely resembled that of the surface salinity. The total uptake of atmospheric CO₂ by the Weddell Gyre in autumn (45 days) was calculated to be 7·10¹² g C. The deep TCO₂ distribution noticeably reflected the different water masses in the region. A new deep TCO₂ maximum was detected in the ACC, which apparently characterizes the boundary between the equatorward flowing Antarctic Bottom Water (AABW) and the Circumpolar Deep Water (CDW). East of the Weddell Gyre, the AABW stratum is much thicker (>2000 m) than more to the west, on the prime meridian (<300 m).     

Discrete element simulation of geogrid-stabilised soil

A particle-based numerical simulation procedure is presented for the generation and calibration of geogrid-stabilised soil on the basis of experimental data. The paper describes how to simulate a biaxial geogrid depending on a specific particle and parallel bond model. Numerical and experimental pull-out tests have been performed to reproduce the pull-out force–strain behaviour of a biaxial geogrid specimen embedded in granular material under special consideration of the grain-size distribution, initial relative density, normal stress state as well as sample installation. Model analysis of soil mobilisation and geogrid deformation is presented to understand the significance of the interlocking effect as key mechanism for soil stabilisation. The procedure can be used for further investigations of the influence and effects of soil stabilisation depending on the significant properties of the interacting components (soils and geogrids).     

Determination of instantaneous sea surface,wave heights,and ocean currents using satellite observations of the global positioning system

Abstract

Using GPS phase observations in the kinematic mode, we are able to achieve centimeter accuracy in relative three‐dimensional coordinates. This could be verified even for fast‐moving sensors in aircraft, such as airborne photogrammetric cameras, at the time of exposure. Sophisticated kinematic software has been developed resolving cycle slips and carrier‐phase ambiguities during motion. To determine the instantaneous sea surface, the GPS receiver is placed in a free‐drifting buoy with the antenna on top. Differencing the 1‐Hz observations, wave heights can be determined as well as velocity and direction of ocean (tidal) currents.

This article deals with the experiences from a test for the practical realization of this proposal. Hardware installation, software, and data analysis are described. Plans to use such an observational scenario of a GPS buoy array in the North Sea for the calibration of the radar altimeter of the European satellite ERS‐1 are presented.     

Metalliferous Sediment and a Silica-Hematite Deposit within the Blanco Fracture Zone,Northeast Pacific

A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO₂ and 11.8% Fe₂O₃. The hematite and opal-CT precipitated from a low-temperature (≥ 115° C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation.

Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO₂ content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity.

Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases.

A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base- and precious-metal-bearing, silica-Fe-oxide-barite deposit. Such deposits are commonly spatially and temporally associated with volcanogenic massive sulfide (VMS) ores. A plot of data for pathfinder elements shows a large hot spot at the northwestern margin of the field, which may mark a region where moderate to high temperature sulfide deposits are forming at depth; further exploration of the hydrothermal field to the northwest is warranted.     

The Rožná uranium deposit (Bohemian Massif, Czech Republic): shear zone-hosted, late Variscan and post-Variscan hydrothermal mineralization

Three major mineralization events are recorded at the Rožná uranium deposit (total mine production of 23,000 t U, average grade of 0.24% U): (1) pre-uranium quartz-sulfide and carbonate-sulfide mineralization, (2) uranium, and (3) post-uranium quartz-carbonate-sulfide mineralization. (1) K–Ar ages for white mica from wall rock alteration of the pre-uranium mineralization style range from 304.5 ± 5.8 to 307.6 ± 6.0 Ma coinciding with the post-orogenic exhumation of the Moldanubian orogenic root and retrograde-metamorphic equilibration of the high-grade metamorphic host rocks. The fluid inclusion record consists of low-salinity aqueous inclusions, together with H₂O-CO₂-CH₄, CO₂-CH₄, and pure CH₄ inclusions. The fluid inclusion, paragenetic, and isotope data suggest that the pre-uranium mineralization formed from a reduced low-salinity aqueous fluid at temperatures close to 300°C. (2) The uraniferous hydrothermal event is subdivided into the pre-ore, ore, and post-ore substages. K–Ar ages of pre-ore authigenic K-feldspar range from 296.3 ± 7.5 to 281.0 ± 5.4 Ma and coincide with the transcurrent reorganization of crustal blocks of the Bohemian Massif and with Late Stephanian to Early Permian rifting. Massive hematitization, albitization, and desilicification of the pre-ore altered rocks indicate an influx of oxidized basinal fluids to the crystalline rocks of the Moldanubian domain. The wide range of salinities of fluid inclusions is interpreted as a result of the large-scale mixing of basinal brines with meteoric water. The cationic composition of these fluids indicates extensive interaction with crystalline rocks. Chlorite thermometry yielded temperatures of 260°C to 310°C. During this substage, uranium was probably leached from the Moldanubian crystalline rocks. The hydrothermal alteration of the ore substage followed, or partly overlapped in time, the pre-ore substage alteration. K–Ar ages of illite from ore substage alteration range from 277.2 ± 5.5 to 264.0 ± 4.3 Ma and roughly correspond with the results of chemical U–Pb dating of authigenic monazite (268 ± 50 Ma). The uranium ore deposition was accompanied by large-scale decomposition of biotite and pre-ore chlorite to Fe-rich illite and iron hydrooxides. Therefore, it is proposed that the deposition of uranium ore was mostly in response to the reduction of the ore-bearing fluid by interaction with ferrous iron-bearing silicates (biotite and pre-ore chlorite). The Th data on primary, mostly aqueous, inclusions trapped in carbonates of the ore substage range between 152°C and 174°C and total salinity ranges over a relatively wide interval of 3.1 to 23.1 wt% NaCl eq. Gradual reduction of the fluid system during the post-ore substage is manifested by the appearance of a new generation of authigenic chlorite and pyrite. Chlorite thermometry yielded temperatures of 150°C to 170°C. Solid bitumens that post-date uranium mineralization indicate radiolytic polymerization of gaseous and liquid hydrocarbons and their derivatives. The origin of the organic compounds can be related to the diagenetic and catagenetic transformation of organic matter in Upper Stephanian and Permian sediments. (3) K–Ar ages on illite from post-uranium quartz-carbonate-sulfide mineralization range from 233.7 ± 4.7 to 227.5 ± 4.6 Ma and are consistent with the early Tethys-Central Atlantic rifting and tectonic reactivation of the Variscan structures of the Bohemian Massif. A minor part of the late Variscan uranium mineralization was remobilized during this hydrothermal event.     

Increase of carbon dioxide in the bottom water of the Weddell Sea, Antarctica

High precision total CO₂ (TCO₂) data are presented from the NW Weddell Sea obtained during two cruises which were 3 years apart. A TCO₂ increase from 1993 to 1996 was observed in the newly formed bottom water, whereas no TCO₂ increase was found in the surrounding water masses. Accompanying this TCO₂ increase in the bottom water was an oxygen decrease. Obviously, bottom water with variable characteristics is produced along the margins of the Weddell Sea. Examination of possible causes leads to the conclusion that the bottom water variability is largely due to varying amounts of Warm Deep Water intruding onto the shelves of the Weddell Sea, thus changing the shelf water end-member of bottom water formation. Analysis of the data, using the observed differences of oxygen to perform a correction, suggested that some part of the TCO₂ increase of the bottom water is due to the increased level of anthropogenic CO₂. The TCO₂ increase of the bottom water is commensurate to a tentative annual increase of about 1 μmol kg⁻¹ in the surface water source of this bottom water. This would agree fairly well with the increase of the partial pressure of CO₂ in the atmosphere.