Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

Palaeovariations in the East-Asian Monsoon Regime Geochemically Recorded in Varved Sediments of Lake Sihailongwan (Northeast China, Jilin Province). Part 2: a 200-Year Record of Atmospheric Lead-210 Flux Variations and its Palaeoclimatic Implications

Palaeovariations of the atmospheric ²¹⁰Pb flux in Northeast China (Long Gang area, Jilin province), quantified by high resolution ²¹⁰Pb measurements on seasonally laminated sediments of Lake Sihailongwan are presented on decadal scale. The mean flux of unsupported ²¹⁰Pb between 1790 and 1970 for the centre of the lake basin is 517 Bq m⁻² yr⁻¹ with maximum deviations between −23% and +27% of this value. Flux rates above this average were found between 1783 and 1813, around 1836, and between 1860 and 1901. The mean ²¹⁰Pb^exc flux rates derived were clearly lower around 1821, 1908, 1930, and 1953. The ²¹⁰Pb^exc flux reached its minimum of 344 Bq m⁻² yr⁻¹ during the period 1977–1982. The atmospheric flux of unsupported ²¹⁰Pb is correlated with the precipitation frequency during the summer monsoon and shows coinciding variability with geochemical proxies that document the groundwater inflow into the lake. Al₂O₃-rich dust of remote provenance scavenged by wet-deposition in the rainy season is the major carrier of the atmospheric ²¹⁰Pb^exc flux.     

Palaeovariations in the East-Asian Monsoon Regime Geochemically Recorded in Varved Sediments of Lake Sihailongwan (Northeast China, Jilin Province). Part 1: Hydrological Conditions and Dust Flux

The varved sediments of the dimictic Lake Sihailongwan (Long Gang mountain area, Jilin Province, Northeast China) represent a palaeoclimatic archive which documents the local precipitation frequency during the summer monsoon, and variations in the aeolian flux of dust with their remote sources in the arid and semi-arid regions of inner Asia. Based on a detailed discussion of sediment genesis in Lake SHL, dust flux rates and palaeohydrological conditions were reconstructed on a decadal scale over the past 220 years. The aeolian influx by dry and wet deposition was quantified and characterised in its chemical composition. Photosynthetic production in the lake is positively correlated with the inflow of nutrient-rich groundwater. The groundwater discharge largely reflects the strength of the summer monsoon. Net accumulation rates for biogenic silica were determined for annually laminated sediments from the centre of the U-shaped lake basin based on sediment data. In a Si-balance model of the modern lake, the depositional flux of biogenic silica could be independently quantified on the base of hydrochemical monitoring data. Comparison of the both estimates allowed to asses the focussing of the particle flux in the lake. Though water retention in Lake SHL is rather high (ca. 30 years), changes in the hydrological conditions are sensitively recorded in the sediments because (i) nutrient-rich groundwater discharges into the productive zone of the lake, (ii) a substantial proportion of the total dissolved Si-inventory of the mixed lake (ca. 30%) is annually consumed by diatom growth, and (3) sediment accumulation is substantially focussed towards the flat bottom of the lake basin. The bulk siliciclastic sediment fraction (ca. 75 wt.%) largely originates from influx of dust of remote provenance. In sediment thin-sections, the dry-deposited dust fraction is microscopically identifiable as seasonal silt layer. Aeolian input by wet-deposition shows a distinctly higher variability than the influx of dust by dry-deposition. As diatom production, wet-deposition of dust is positively correlated with the rainfall during the summer monsoon. The inferred positive correlation between rainfall and dust flux during the summer monsoon implies that dust deposition is determined by the out-wash efficiency of mineral particles for a permanent high atmospheric dust concentration over Northeast China in the last 220 years.     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa: I. Styles of brecciation and mineralization

The Pering deposit on the Ghaap Plateau, Northwestern Province, South Africa, was the largest of several Zn–Pb occurrences hosted by Neoarchean platform dolostones of the Transvaal Supergroup. With a Paleoproterozoic mineralization age, these occurrences are widely regarded as the oldest representatives of Mississippi Valley-type Pb–Zn deposits. Hosting an initial resource of 18 Mt at an average grade of 3.6 wt% Zn and 0.6 wt% Pb, the Pering deposit was mined from 1984 until its final closure at the end of November 2002. In this study, available geological and grade distribution maps were evaluated and complemented by the examination of mining-related outcrops, drill core, and a large set of ore and host rock samples. Four different styles of brecciation can be distinguished at the Pering deposit: (1) pyritic rock matrix breccia; (2) chemical wear breccia; (3) mosaic breccia; and (4) crackle breccia. Geological and mineral paragenetic observations on these different breccia types suggest that the formation of the Pering deposit commenced with an initial stage of hydrothermal karstification. Large volumes of pyritic rock matrix breccia formed by wall rock collapsing into the open space attributed to carbonate dissolution. This stage of hydrothermal karstification acted as ground preparation for the subsequent mineralization event. By the upward advance of the hydrothermal karstification process, fluid reservoirs in the previously undisturbed dolostone host rock succession were tapped, ultimately leading to fluid mixing. Hydrothermal sulphides are the most abundant where fluid mixing was most effective, i.e. along the outer and upper margins of the breccia bodies, and in stratabound zones along permeable host rock units. Chemical wear brecciation and formation of large volumes of fine-grained replacive sphalerite mineralization mark the early stage of hydrothermal Zn–Pb mineralization associated with this fluid mixing. The fine-grained stage of sulphide mineralization was succeeded by very coarse-grained open-space-infill mineralization. The latter is very uniform across the entire deposit and typically cements mosaic and crackle breccia, but also fills remaining open space within chemical wear brecciated portions of the deposit.     

Phytoplankton, nutrients, and transparency in Danish coastal waters

We present a comparative analysis of 1400 data series of water chemistry (particularly nitrogen and phosphorus concentrations), phytoplankton biomass as chlorophylla (chla) concentrations, concentrations of suspended matter and Secchi depth transparency collected from the mid-1980s to the mid-1990s from 162 stations in 27 Danish fjords and coastal waters. The results demonstrate that Danish coastal waters were heavily eutrophied and had high particle concentrations and turbid waters. Median values were 5.1 μg chla 1⁻¹, 10.0 mg DW 1⁻¹ of suspended particles, and Secchi depth of 3.6 m. Chlorophyll concentration was strongly linked to the total-nitrogen concentration. The strength of this relationship increased from spring to summer as the concentration of total nitrogen declined. During summer, total nitrogen concentrations accounted for about 60% of the variability in chlorophyll concentrations among the different coastal systems. The relationship between chlorophyll and total phosphorus was more consistant over the year and correlations were much weaker than encountered for total nitrogen. Secchi depth could be predicted with good precision from measurements of chlorophyll and suspended matter. In a multiple stepwise regression model with In-transformed values the two variables accounted for most of the variability in water transparency for the different seasons and the period March–October as a whole (c. 80%). We were able to demonstrate a significant relationship between total nitrogen and Secchi depth, with important implications for management purposes.     

Methodology for construction, calibration and validation of a national hydrological model for Denmark

An integrated groundwater/surface water hydrological model with a 1 km² grid has been constructed for Denmark covering 43,000 km². The model is composed of a relatively simple root zone component for estimating the net precipitation, a comprehensive three-dimensional groundwater component for estimating recharge to and hydraulic heads in different geological layers, and a river component for streamflow routing and calculating stream–aquifer interaction. The model was constructed on the basis of the MIKE SHE code and by utilising comprehensive national databases on geology, soil, topography, river systems, climate and hydrology. The present paper describes the modelling process for the 7330 km² island of Sjælland with emphasis on the problems experienced in combining the classical paradigms of groundwater modelling, such as inverse modelling of steady-state conditions, and catchment modelling, focussing on dynamic conditions and discharge simulation. Three model versions with different assumptions on input data and parameter values were required until the performance of the final, according to pre-defined accuracy criteria, model was evaluated as being satisfactory. The paper highlights the methodological issues related to establishment of performance criteria, parameterisation and assessment of parameter values from field data, calibration and validation test schemes. Most of the parameter values were assessed directly from field data, while about 10 ‘free’ parameters were subject to calibration using a combination of inverse steady-state groundwater modelling and manual trial-and-error dynamic groundwater/surface water modelling. Emphasising the importance of tests against independent data, the validation schemes included combinations of split-sample tests (another period) and proxy-basin tests (another area).     

Gravity reduction with three-dimensional atmospheric pressure data for precise ground gravity measurements

The redistribution of air masses induces gravity variations (atmospheric pressure effect) up to about 20 μgal. These variations are disturbing signals in gravity records and they must be removed very carefully for detecting weak gravity signals. In the past, different methods have been developed for modelling of the atmospheric pressure effect. These methods use local or two-dimensional (2D) surface atmospheric pressure data and a standard height-dependent air density distribution. The atmospheric pressure effect is consisting of the elastic deformation and attraction term. The deformation term can be well modelled with 2D surface atmospheric pressure data, for instance with the Green's function method. For modelling of the attraction term, three-dimensional (3D) data are required. Results with 2D data are insufficient.From European Centre for Medium-Range Weather Forecasts (ECMWF) 3D atmospheric pressure data are now available. The ECMWF data used here are characterised by a spacing of Δ and Δλ = 0.5°, 60 pressure levels up to a height of 60 km and an interval of 6 h. These data are used for modelling of the atmospheric attraction term. Two attraction models have been developed based on the point mass attraction of air segments and the gravity potential of the air masses. The modelling shows a surface pressure-independent part of gravity variations induced by mass redistribution of the atmosphere in the order of some μgal. This part can only be determined by using 3D atmospheric pressure data. It has been calculated for the Vienna Superconducting Gravimeter site.From this follows that the gravity reduction can be improved by applying the 3D atmospheric attraction model for analysing long-periodic tidal waves including the polar tide. The same improvement is expected for reduction of long-term absolute gravity measurements or comparison of gravity measurements at different seasonal times. By using 3D atmospheric pressure data, the gravity correction can be improved up to some μgal.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.