Stratigraphic sequence, elemental concentrations and heavy metal pollution in Holocene sediments from the Tinto-Odiel Estuary, southwestern Spain

 The Holocene filling of the Tinto-Odiel Estuary comprises seven lithofacies over a Mio-Pliocene substrate. The sequence includes three system tracts: lowstand system (10 000 to 8700 years BP), transgressive system (8700 to 7000 years BP), and regressive system (7000 to Recent). Twenty sediment samples from the 50-m borehole were analyzed for their major components and minor element concentrations. Two multivariate analysis methods, principal component analysis and cluster analysis, were performed in the analytical data set to help visualize the sample clusters and the element associations. Samples corresponding to unpolluted, pre-mining sediments are clearly separated by cluster analysis, mainly as a result of the low content in sulphide-associated heavy metals such as Cu, Zn, As, Ag, and Pb. So, these sediments may be utilized as a background for geochemical analysis (bulk sample) in other adjacent estuaries, both in sandy and silty-clayey sediments. As a consequence of large-scale mining and smelting operations occurred since prehistoric times on the river banks, a rapid rise in the metal pollution was found in the upper 2.5 m of the natural filling, with values exceeding up to ten times the natural background levels. In addition, since the mid-1960s, large amounts of waste and pollutant effluents have been discharged from industries located around the estuary, increasing the heavy metal content in the last 0.3 m of the natural sedimentation. Received: 18 August 1997 · Accepted: 19 January 1998     

Historical analysis of heavy metal pollution in three estuaries on the north coast of Galicia (NW Spain)

This research focuses on the development of metal pollution in sediment cores from three estuaries in Northwest Spain: Viveiro, Ortigueira and Barqueiro. Pb, Cu, Co, Cr, Cd and Zn and total organic carbon were assessed using principal component analysis (PCA) in order to obtain background values, measure pollution levels and identify pollution sources. Results were interpreted by considering the local industrial history, grain size and C/N relationship. The pollution levels obtained bear a strong resemblance to those documented for of a moderately industrialised area. PCA identifies factors that reflect mainly temporal associations with metals. Sedimentation rates between 0.9 and 1.1 cm/year were determined. In Viveiro core levels of Cr pollution are associated with tanneries. In Ortigueira, high core levels of Cu and Co are linked to mining, and Cr levels to adjacent ultramafic rocks. Erosion of Holocene sediment causes high values of Co and Cr in the Barqueiro core. Cu increase in the three estuaries is related to fungicide use since 1910. Sea level rise appears to be affecting the marine characteristics of the sediments in Barqueiro. In Viveiro, the nature of the sediment reflects engineering work and land reclamation.     

Distribution of heavy metals in the Piscinas beach sediments (SW Sardinia, Italy)

We have studied sediments of the Piscinas beach (SW Sardinia, Italy), which is supplied by two streams that wash mine dumps of abandoned lead and zinc mines at Montevecchio and Ingurtosu, situated inland from the supply basin of the beach itself. A study of the texture, mineralogy and geochemistry of the sediments was conducted for the purpose of assessing the possible influence of the mine waste on the composition of the sediments, looking for any anomalous enrichments in heavy metals. Furthermore, to evaluate and quantify metal release into the sea, samples of Posidonia oceanica, a bioaccumulator marine plant, were also examined. The results indicate that the distribution of heavy metals in the foreshore sediments is particularly affected by the contribution of the streams, while in the shoreface the distribution is affected by the currents that disperse the sediments both out to sea and southwards. The metal contents of the Posidonia oceanica are correlated with the different stages of activity of the mines. Received: 28 January 1998 · Accepted: 22 April 1998     

Source of pollution as a factor controlling distribution of heavy metals in bottom sediments of Chechło River (south Poland)

 The influence of sources of effluents on pollution of bottom sediments of the small Chechło River (23 km long, mean discharge 1.5 m³ s^–1) in southern Poland was examined through analysis of heavy metals distribution in transverse and longitudinal cross sections. Underground waters from a Pb–Zn mine cause very high concentrations of Zn, Cd, and Pb in both fractions investigated (<1 mm and <0.063 mm) of sediments in the active channel zone, whereas sedimentation of huge amounts of suspended matter discharged from oil refinery cause concentrations of heavy metals in fine fractions rather uniform in cross sections. In the lowest reach, with relatively reduced contamination, the highest concentration both in fine and coarse fractions occurs close to the river banks and in the deepest points of the channel. The lowest concentrations have been found at the points of strongest reworking and accumulation of sandy material in the riverbed. Received: 25 April 1995 · Accepted: 11 September 1995     

Weathered bedrock as a source of sand and gravel aggregate in north-eastern New South Wales, Australia

 The most commonly recognized sources of sand and gravel aggregate are the deposits of coastal, fluvial and glacial sedimentary processes. It is not commonly recognized that weathered bedrock is also an important source of sand and gravel aggregate. In the case of weathered sedimentary bedrock the product may be indistinguishable from modern sedimentary materials and deposits may be misidentified. Batson's quarry is a major sand and gravel aggregate resource for the rapidly developing region of north-eastern New South Wales. The deposit has previously been assumed to be a young sedimentary deposit, but detailed field examination and comparison with surrounding rock types indicates that it has formed from weathered Mesozoic sandstone bedrock. The extraction of weathered bedrock aggregate deposits has distinctive environmental implications because, unlike sedimentary aggregates, they are not restricted by the geometry of sedimentary environments and do not necessarily interfere with surface drainage systems. This study shows that the recognition of the geological origin of a resource is essential in order to determine its potential geographical extent, and thereby maximize its utilization and minimize land use conflict. Received: 3 January 1996 / Accepted: 1 November 1996     

Mine waste dumps and heavy metal pollution in abandoned mining district of Boccheggiano (Southern Tuscany, Italy)

 Mining activity in the Boccheggiano-Fontalcinaldo area (Southern Tuscany) dates back at least to the 16th century AD and lasted up to very recent times. Copper-rich hydrothermal veins, massive pyrite deposits, and their gossans were exploited. Two mine waste dumps (Fontalcinaldo, Fontebona), one flotation tailings impoundment (Gabellino), and one roasting/smelting waste dump (Merse-Ribudelli) in the study area were selected to ascertain the environmental effects of such protracted mining activity. Primary waste mineralogy is mainly characterized by pyrite, gypsum, quartz, carbonates, chlorites, and micas. Secondary oxidation mineralogy includes Fe and Cu sulfates and hydroxy sulfates, Cu carbonates, Fe and Al oxyhydroxides, and other phases [neogenic cassiterite at Fontalcinaldo; probable calkinsite, (Ce,La)₂(CO₃)₃· 4H₂O, at Fontebona]. Mine waste samples show extremely variable contents of toxic elements (Cu, Pb, Zn, Bi, Cd, As), with average values in the order of hundreds to thousands of parts per million (except for Bi and Cd). In some samples, the abundance of proper minerals of these metals cannot account for the entire metal load. Conceivably, either solid solution substitutions or adsorption processes contribute to the intake of released metals into newly formed minerals. Release and transport of pollutants was affected to variable degrees by acid-neutralization processes. The highest metal and acid concentrations occur close to the investigated wastes and rapidly decrease moving downstream some hundreds of meters or less, with the partial exception for Mn and Fe. Other than dilution effects, this phenomenon may be ascribed to metal adsorption and precipitation of solid phases. Received: 16 April 1995 · Accepted: 14 December 1995     

Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x )2SiO4, 0.2 ≤ x ≤ 1.0

 The variation of the oxygen content in olivines, (Fe _x Mg_{1− x} )₂SiO₄, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO₂ and N₂ and, at a few spots at the bottom of the sample stack, also with SiO₂. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe³⁺ ions on M sites and Fe³⁺ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO₂ or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

Stable isotopes and heavy metal distribution in Dreissena polymorpha (Zebra Mussels) from western basin of Lake Erie, Canada

 Dreissena polymorpha is an exotic freshwater bivalve species which was introduced into the Great Lakes system in the fall of 1985 through the release of ballast water from European freighters. Utilizing individual growth rings of the shells, the stable isotope distribution (δ¹⁸O and δ¹³C) was determined for the life history of selected samples which were collected from the western basin of Lake Erie. These bivalves deposit their shell in near equilibrium with the ambient water and thus reflect any annual variation of the system in the isotopic records held within their shells. Observed values for δ¹⁸O range from -6.64 to –9.46‰ with an average value of –7.69‰ PDB, while carbon values ranged from –0.80 to –4.67‰ with an average value of –1.76‰ PDB. Dreissena polymorpha shells incorporate metals into their shells during growth. Individual shell growth increments were analyzed for Pb, Fe, Mg, Mn, Cd, Cu, and V concentrations. The shells show increased uptake of certain metals during periods of isotopic enrichment which correspond with warmer water temperatures. Since metals are incorporated into the shells, the organism may be useful as a biomonitor of metal pollution within aquatic environments. Received: 31 October 1996 · Accepted: 21 May 1997     

Channel processes as a factor controlling accumulation of heavy metals in river bottom sediments: consequences for pollution monitoring (Upper Silesia, Poland)

 An evaluation of the influence of channel processes (erosion, accumulation, processing of channel sediments) on the dispersal of heavy metals in bottom sediments was carried out in the channels of the Sztoła and Biała Przemsza rivers in Upper Silesia, Poland. These rivers receive waters from a Zn and Pb mine. Mine waters transport a large amount of fine-grained sediments contaminated with heavy metals. The polluted material is accumulated in these stream courses and mixed with nearly homogeneous sandy sediment derived from erosion of the river banks and bed. Because these alluvia are easily set in motion, the distribution of heavy metal concentration in the channel in fraction <1 mm reflects differences in physical processes of sedimentation in its cross-section. The minimal values in active channel and maximal in the near-bank zone are typical for those channel sections where heavy metals, present in a solid state, are transported as a suspended load (normally the largest part of a polluted river course). In short sections heavy metals associated with the grains of a large mass which has accumulated in the active channel are transported as a bed load and the typical distribution pattern is reversed (in fractions both <1 mm and <0.063 mm). Such regularities can be disturbed in localities where strong, turbulent flow or frequent eddying occur and Mn oxides and hydrooxides and associated elements precipitate. The smallest variation in heavy metal concentration in the homogenous, fine-grained bank sediments which are trapped by plants below water level is a feature which recommends these localities as being the most suitable for monitoring of river pollution. Received: 11 November 1997 · Accepted: 12 March 1998     

Geochemistry of Cu, Co, Ni, Zn, Cd and Cr in the surficial sediments of a tropical estuary, southwest coast of India: a granulometric approach

 Geochemical characteristics of six trace metals – Cu, Co, Ni, Zn, Cd and Cr – in the bulk sediment and sand, silt and clay fractions of a tropical estuary on the southwest coast of India have been studied and discussed. In bulk sediment, the trace metal concentration is controlled mainly by the textural composition of the sample. Mud, sandy mud and sandy silt register higher concentrations of trace metals than that in sand-dominant sediments. The granulometric partitioning studies also re-affirmed the role of particle size in enriching the trace metals. The silt and clay fractions exhibit 7–8 times the enrichment of Cu and Cd compared to that in sand. The enrichment factors of Zn, Cr, Ni and Co in the silt and clay fractions, compared to that in sand, are 5–6, 4–5, 2–5 and 2–3 times, respectively. The trace metals in the sand fraction, particularly Ni and Cr, exhibit strong positive correlation with the heavy mineral content of the samples. It clearly indicates a heavy mineral pathway to the trace metals in the sand fraction. Cu and Co in silt and clay fractions exhibit a marked decrease towards the high saline zones of the estuary. This is attributed to the desorption of Cu and Co from particulate phases during estuarine mixing. Contrary to Cu and Co, the content of Zn in the clay fraction shows a marginal increase towards the estuarine mouth. This could be explained by the influx of Zn-rich contaminant discharges from Zn-smelting industries located slightly north of the estuarine mouth. The released Zn will effectively be held in the lattices of the clay mineral montmorillonite, which also exhibits a marked increase towards the estuarine mouth. The anomalously high values of Cd in some places of the Central Vembanad estuary is attributed to the local pollution. Received: 10 July 1995 · Accepted: 3 June 1996     

Heavy metal pollution in freshly deposited sediments of the Yamuna River (the Ganges River tributary): a case study from Delhi and Agra urban centres, India

 The Yamuna River sediments, collected from Delhi and Agra urban centres, were analysed for concentration and distribution of nine heavy metals by means of atomic adsorption spectrometry. Total metal contents varied in the following ranges (in mg/kg): Cr (157–817), Mn (515–1015), Fe (28,700–45,300), Co(11.7–28.4), Ni (40–538), Cu (40–1204), Zn (107–1974), Pb (22–856) and Cd (0.50–114.8). The degree of metal enrichment was compared with the average shale concentration and shows exceptionally high values for Cr, Ni, Cu, Zn, Pb and Cd in both urban centres. In the total heavy metal concentration, anthropogenic input contains 70% Cr, 74% Cu, 59% Zn, 46% Pb, 90% Cd in Delhi and 61% Cr, 23% Ni, 71% Cu, 72% Zn, 63% Pb, 94% Cd in Agra. A significant correlation was observed between increasing Cr, Ni, Zn, and Cu concentrations with increasing total sediment carbon and total sediment sulfur content. Based on the Müller's geoaccumulation index, the quality of the river sediments can be regarded as being moderately polluted to very highly polluted with Cr, Ni, Cu, Zn, Pb and Cd in the Delhi and Agra urban centres. The present sediment analysis, therefore, plays an important role in environmental measures for the Yamuna River and the planning of these city centres. Received: 21 June 1999 · Accepted: 1 October 1999     

Background concentrations of heavy metals in aquatic bryophytes used for biomonitoring in basaltic areas (a case study from central France)

 Studies were made of the aquatic bryophytes Fontinalis antipyretica Hedw., Platyhypnidium rusciforme (Neck.)Fleisch and Chiloscyphus sp. (Hoffm.)Dum. from streams embedded in basaltic rocks (Le Puy, central France). Water from these streams possessed elevated levels of Cu, Zn, Sr, V, Ba, Ni and Co, reflecting the geochemistry of the basalts, a basic type of igneous rocks containing elevated levels of these elements. The concentration of elements in bryophytes is correlated to the chemical composition of water of their sampling sites. Contents of trace elements in plants were higher than background values. The elevated levels of these elements possibly caused disturbances in the ionic equilibrium within the bryophytes. The molar ratio between contents of Ca and Mg in water (from 0.44 to 1) was different from that typical for natural water. Received: 16 September 1998 · Accepted: 17 December 1998     

Point defects and cation tracer diffusion in (Ti x Fe 1?x ) 3?δ O4 1. Non-stoichiometry and point defects

 The deviation from stoichiometry, δ, in spinel solid solutions of the type (Ti _x Fe _1−x )_3−δ O₄ with x=0.1, 0.2 and 0.25 was studied thermogravimetrically as a function of oxygen activity, a _O2, at 1100, 1200 and 1300 ^∘C. The experimental results, S-shaped curves for δ vs. log a_O2, are presented and discussed with regard to the type of point defects prevailing under different conditions in the deviation from stoichiometry. It is concluded that cation vacancies are the predominant point defects at high oxygen activities, while cation interstitials prevail at low oxygen activities. The temperature and composition dependencies of point defect concentrations are also discussed. Received: 1 October 1996 / Accepted: 15 September 2002 Acknowledgements The authors thank the US Department of Energy for support of this work under Grant no. DE-FGO2–88ER45357. This work made use of the Cornell Center of Materials Shared Experimental Facilities, supported through the National Science Foundation Materials Research Science and Engineering Centers program (DMR-0079992).     

SiO bonded interactions in coesite: a comparison of crystalline, molecular and experimental electron density distributions

Bond critical point properties of electron density distributions calculated for representative Si₅O₁₆ moieties of the structure of coesite are compared with those observed and calculated for the bulk crystal. The values calculated for the moieties agree with those observed to within ∼5%, on average, whereas those calculated for the crystal agree to within ∼10%. As the SiOSi angles increase and the SiO bonds shorten, there is a progressive build-up in the calculated electron density along the bonds. This is accompanied by an increase in both the curvatures of the electron density, both perpendicular and parallel to each bond, and the Laplacian of the electron density distribution at the bond critical points. The cross sections of the bonds at the critical points become more circular as the angle approaches 180o. Also, the bonded radius of the oxide anion decreases about twice as much as that of the Si cation as the SiO bond length decreases and the fraction of s-character of the bond is indicated to increase. A knowledge of electron density distributions is central to our understanding of the forces that govern the structure, properties, solid state reactions, surface reactions and phase transformations of minerals. The software (CRYSTAL95 and TOPOND) used in this study to calculate the bond critical properties of the electron density and Laplacian distributions is bound to promote a deeper understanding of crystal chemistry and properties. Received: 23 February 1998 / Revised, accepted: 16 July 1998     

Geochemical behaviour and relative mobility of metals (Mn, Cd, Zn and Pb) in recent sediments of a retention pond along the A-71 motorway in Sologne, France

 Retention ponds have been dug along some of the motorways in France to minimize environmental pollution by keeping pollutants from spreading over the surrounding area. In the current work, eight core samples were collected from the bottom of a retention pond located along the A-71 motorway in Sologne to study the pollution of sediment by heavy metals and their diagenetic behaviour. The vertical concentration profiles of metals (Pb, Zn, Cd, Fe and Mn) in sediment as well as in interstitial water were determined. Especially in the case of the sediment, a sequential extraction method was employed to investigate how the movement of each metal is associated with the other metals and with other solid phases such as organic matter. In addition, to investigate the relative mobility of the metals, the distribution coefficients (K_D) were also determined. The concentrations of the metals were always found to be highest in the topmost layer of sediment. This so-called surface enrichment is caused by a substantial increase of the non-detrital fraction of these metals at the sediment surface. For instance, the accumulation of Pb and Zn is associated with the increase in the "fraction II" in the sequential extraction. The accumulation of Cd at the surface (0–2 cm) is partly due to the liberation of Cd from the particles during early diagenesis. However, the major factor contributing to the accumulation of Cd at the sediment surface is attributed to the dissolution of Cd from polluted roadside soil during the periods of rainstorms and its subsequent redeposition on the sediment surface after being carried to the retention pond. K_D values for Zn and Cd were found to decrease with depth, while K_D values for Pb increased. Based on the K_D values, the relative mobilities of the studied metals were determined to be as follows: Mn>Zn>Cd>Pb, for the upper layer, and Mn>Cd>Zn>Pb, for the layers below. Received: 28 October 1996 / Accepted: 21 November 1996     

Standardization of metal concentrations in sediments using regression residuals: an example from a large lake in Florida, USA

 A new method of standardizing metal concentrations in sediments was tested on samples from Lake Miccosukee, a large karstic lake in north Florida. Metal concentrations were analyzed in 222 sediment samples from 26 cores representing 9 sampling sites in the lake. Measured sedimentation rates in the lake are low. Percent organic matter strongly increases upward in all the cores. The C/N ratio remains constant throughout all the samples, with a mean value of about 13, regardless of depth or location. All of the geochemical variables are at least approximately log-normally distributed; thus, log-log or semi-log scattergrams were used and the data were log-transformed before statistical calculations were performed. Some elements (Mn, Zn, Hg, Cu, and Ca) are primarily associated with the organic fraction; others (La, Cr, Sr, and Ba) are clearly related to the terrigenous fraction; others show affinities for both fractions. Consequently, no bivariate scattergrams or plots of ratio versus depth – commonly used for standardization by plotting or ratioing a reference element (such as Al) to an element of interest – were found to be adequate for standardization of this dataset. The best method for standardization was found to be one based on multivariate (trivariate) linear regression, using log Al and log C as the independent variables (reference elements representing terrigenous and organic fractions, respectively), and the log of the element of interest as the dependent variable. Residuals (deviations) from the best-fit linear surface were then plotted versus depth in the cores to accomplish the standardization. The results indicate that, with the possible exception of Mn at two sites, there is little evidence of anthropogenic input of trace elements to the lake, and most trace-element concentrations in the lake can be considered as valuable baseline information. A significant finding is that different and erroneous conclusions might have been reached if other standardization methods, not based on trivariate regression, had been employed. Received: 28 August 1997 · Accepted: 24 November 1997     

Chemical composition of landfill leachate in a karst area with a Mediterranean climate (Marbella, southern Spain)

 Between March 1994 and April 1997, the physical and chemical parameters and chemical composition of the urban solid waste leachate of the Marbella landfill (southern Spain) were determined. The data obtained show an ammonium and sodium chloride and bicarbonate type, a pH>7 and high mineralization, effectively described by the following parameters: Na⁺, K⁺, NH₄ ⁺, Cl^– and alkalinity. The chemical composition depends on the rainfall: in dry years, the mineralization and component concentrations have values as much as double those found in normal rainfall years. After storm events, a major and rapid dilution (within several hours) is seen in the leachate. Received: 28 January 1998 · Accepted: 2 June 1998     

Water vulnerability assessment in karst environments: a new method of defining protection areas using a multi-attribute approach and GIS tools (EPIK method)

 Groundwater resources from karst aquifers play a major role in the water supply in karst areas in the world, such as in Switzerland. Defining groundwater protection zones in karst environment is frequently not founded on a solid hydrogeological basis. Protection zones are often inadequate and as a result they may be ineffective. In order to improve this situation, the Federal Office for Environment, Forests and Landscape with the Swiss National Hydrological and Geological Survey contracted the Centre of Hydrogeology of the Neuchatel University to develop a new groundwater protection-zones strategy in karst environment. This approach is based on the vulnerability mapping of the catchment areas of water supplies provided by springs or boreholes. Vulnerability is here defined as the intrinsic geological and hydrogeological characteristics which determine the sensitivity of groundwater to contamination by human activities. The EPIK method is a multi-attribute method for vulnerability mapping which takes into consideration the specific hydrogeological behaviour of karst aquifers. EPIK is based on a conceptual model of karst hydrological systems, which suggests considering four karst aquifer attributes: (1) Epikarst, (2) Protective cover, (3) Infiltration conditions and (4) Karst network development. Each of these four attributes is subdivided into classes which are mapped over the whole water catchment. The attributes and their classes are then weighted. Attribute maps are overlain in order to obtain a final vulnerability map. From the vulnerability map, the groundwater protection zones are defined precisely. This method was applied at several sites in Switzerland where agriculture contamination problems have frequently occurred. These applications resulted in recommend new boundaries for the karst water supplies protection-zones. Received: 27 October 1997 · Accepted: 4 July 1998     

Determining sedimentation ages of high-grade metamorphic gneisses by their palynological record: a case study in the northern Schwarzwald (Variscan Belt, Germany)

 In the northern Schwarzwald (Moldanubian Zone of the Variscan belt), paragneisses drilled from approximately 2500 m depth at the Bühl-1 drilling site have experienced amphibolite-facies metamorphism and were later partly transformed to mylonites under greenschist-facies conditions. Completely graphitised acritarchs and chitinozoans were recovered from these paragneisses and mylonitic gneisses. Whereas both groups of palynomorphs give evidence of a marine depositional environment, only the chitinozoans are stratigraphically useful in this case and indicate a Paleozoic age. Previous findings of acritarchs in a different high-grade metamorphic gneiss unit within the Schwarzwald indicate an Upper Proterozoic marine sedimentation age. The spectrum of palynomorphs found thus far in the Schwarzwald in combination with petrological data suggests that within the Moldanubian domain of the Armorican microplate, rocks with different sedimentary records later experienced diverging prograde metamorphic histories. In general, the results reveal that palynological studies in combination with petrological data are a promising tool for reconstructing pre-orogenic settings in collisional belts. Received: 17 July 1998 / Accepted: 19 January 1999